TWI786200B - Formation method of anti-glare hard coating - Google Patents

Abstract

The object of the present invention is to provide a method for forming an anti-glare hard coat layer having a concavo-convex shape capable of exhibiting good anti-glare properties and having excellent scratch resistance. The present invention relates to a method for forming an anti-glare hard coating, which is provided with an anti-glare hard coating with concave-convex shapes on at least one side of a transparent support substrate, comprising the following steps: a template substrate manufacturing step, It manufactures a template base material with concave-convex shapes on the surface; a coating step, which coats a hard coating composition on one side of the transparent support base material to form an unhardened hard coat layer; a surface contact step, which uses the aforementioned template The uneven surface of the substrate and the surface of the uncured hard coat layer are facing each other so that the two substrates are in surface contact; a hardening step of irradiating active energy rays to harden the uncured hard coat layer; and, a peeling step, It peels the template base material from the hardened hard coat layer; the aforementioned hard coat composition includes polymerizable unsaturated group-containing oligomers or polymers with a weight average molecular weight in the range of 1,000 to 200,000; the unevenness of the aforementioned template base material The peeling strength of the surface contact part of the shape surface and the unhardened hard coating surface is in the range of 0.01~2N/25mm; The strength is in the range of 0.005~1.5N/25mm; and, in the surface contact step between the concave-convex shape surface of the template base material and the unhardened hard coating surface, the pressing pressure is 0.001~5MPa, and the pressing pressure is within the aforementioned range. The embossed shape transfer rate is 75~100%.

Description

Formation method of anti-glare hard coating

The present invention relates to a method for forming an anti-glare hard coating that is especially applicable to optical laminated components such as displays.

Displays are used in computers, televisions, mobile phones, portable information terminals (tablet computers, mobile devices, and electronic notebooks, etc.), as well as digital meters, instrument panels, navigation, control panels, center clusters, and heater controls. Panels and other automotive display panels and other fields. In these displays, an anti-glare (AG: Anti Glare) layer for roughening the surface is often provided on the surface of the display. By setting the anti-glare layer on the surface of the display, the light from the outside can be diffused by the concave-convex shape of the surface of the anti-glare layer, so that the outline of the image reflected on the surface of the display can be blurred. Thereby, the visibility of the reflected image on the surface of the display can be reduced, thereby eliminating the obstacle to the visibility of the screen caused by the reflection of the reflected image when the display is in use.

As mentioned above, the anti-glare layer utilizes the concave-convex shape of the surface to perform the function of diffusing light from the outside. Therefore, the anti-glare layer is often provided on the surface layer side such as the outermost layer of the optical laminated member. In particular, for display devices such as high-resolution displays in recent years, the pitch of light emitted by the display becomes finer. Therefore, a finer and denser concave-convex shape is required in order to maintain the sharpness of the image.

In addition, excellent scratch resistance and durability are also required for the surface layer of an optical layered member such as a display. For example, when the scratch resistance of the surface layer is not good, it is easy to scratch and greatly reduce the visibility of the display.

For example, Japanese Unexamined Patent Publication No. 2011-69913 (Patent Document 1) describes an anti-glare film, which is characterized in that an anti-glare layer with fine concavities and convexities is provided on the transparent plastic film substrate, and the anti-glare layer on the substrate is The outermost surface of the anti-glare layer has a scratch-resistant layer, the average film thickness of the scratch-resistant layer is 0.03-0.50 μm, and the scratch-resistant layer is formed of a hardening composition, and the hardening composition contains at least the component (A ) Inorganic microparticles with an average particle diameter of 40 nm to 100 nm, (B) inorganic microparticles with an average particle diameter of 1 nm to less than 40 nm, (C) ionizing radiation-curable multifunctional monomers, and (D) organic polymer tackifiers, And it does not substantially contain polymerizable fluorine-containing binders. As means for solving the above-mentioned problems, a method of separately providing an anti-glare layer and a scratch-resistant layer as disclosed in Patent Document 1 can be cited. However, when the anti-glare layer and the scratch-resistant layer are separately provided, the number of layers will increase. Since each functional layer is provided separately, the difference in refractive index of each layer may cause refraction at the interlayer surface, which may affect visibility.

Japanese Patent Application Laid-Open No. 2007-183653 (Patent Document 2) describes an anti-glare hard-coated film whose surface has a micro-concave-convex structure, has a good anti-glare effect and has excellent scratch resistance. Hard-coat property, the anti-glare hard-coat film is characterized in that an active energy ray-curable resin film layer is provided on at least one side of a substrate made of transparent plastic, and an active energy ray-curable resin film layer is provided on the side of the active energy ray-curable resin film layer. The surface has a concave-convex structure composed of two types of fine concave-convex with different concave-convex height differences (claim 1). In addition, Patent Document 2 also describes a method for producing the above-mentioned anti-glare hard-coated film, which comprises coating the active energy ray-curable resin on at least one side of a substrate, and irradiating the active energy ray-curable resin film layer. The active energy rays harden the active energy ray-curable resin film layer, and then apply at least one of sandblasting or embossing to form the cured active energy ray-curable resin film layer on the base material, Its surface has a concave-convex structure composed of two types of fine concave-convex with different average height differences of the concave-convex (claim 6). Prior art literature patent documents

[Patent Document 1] Japanese Unexamined Patent Publication No. 2011-69913 [Patent Document 2] Japanese Unexamined Patent Publication No. 2007-183653

Summary of the invention The problem to be solved by the invention The present invention can solve the above-mentioned conventional problems, and aims to provide a method for forming an anti-glare hard coat layer. The anti-glare hard coat layer has a concavo-convex shape that can exhibit good anti-glare properties and has excellent scratch resistance. means to solve problems

In order to solve the above-mentioned problems, the present invention provides the following aspects. [1] A method for forming an anti-glare hard coating, which is provided with an anti-glare hard coating with concave-convex shapes on at least one side of a transparent support substrate, comprising the following steps: a template substrate manufacturing step, which Making a template base material with a concave-convex shape on the surface; a coating step of coating a hard coating composition on one side of the transparent support base material to form an unhardened hard coat layer; a surface contact step of using the aforementioned template base a direction in which the concave-convex shape surface of the material is opposed to the surface of the unhardened hard coat layer to bring the two substrates into surface contact; a hardening step of irradiating active energy rays to harden the unhardened hard coat layer; and a peeling step of exfoliating The template base material is peeled off from the hardened hard coat layer; and, the aforementioned hard coat composition includes polymerizable unsaturated group-containing oligomers or polymers with a weight average molecular weight in the range of 1,000 to 200,000; the unevenness of the aforementioned template base material The peeling strength of the surface contact part of the shape surface and the unhardened hard coating surface is in the range of 0.01~2N/25mm; The strength is in the range of 0.005~1.5N/25mm; and in the surface contact step between the concave-convex shape surface of the template base material and the unhardened hard coating surface, the pressing pressure is 0.001~5MPa, and the concave-convex when the pressing pressure is in the aforementioned range The shape transfer rate is 75~100%. [2] A method for forming an anti-glare hard coat layer, wherein the concave-convex shape on the surface of the template substrate is formed by applying a coating composition for forming concave-convex shapes containing the first component and the second component, and then using The first component and the second component are phase-separated. [3] A method for forming an anti-glare hard coat, wherein the aforementioned hard coat composition comprises: the aforementioned polymerizable unsaturated group-containing oligomer or polymer having a weight average molecular weight in the range of 1,000 to 200,000; a polymerizable unsaturated group-containing monomer having a saturated group equivalent of 90 to 500 g/eq; The amount of the oligomer or polymer is 15-85 parts by mass, and the amount of the aforementioned polymerizable unsaturated group-containing monomer is 85-15 parts by mass. [4] A method for forming an antiglare hard coat layer, wherein the polymerizable unsaturated group of the polymer containing a polymerizable unsaturated group is selected from the group consisting of acryl and methacryl species or more than one species. [5] A method for forming an anti-glare hard coat layer, wherein the hardness of the anti-glare hard coat layer is 3H or higher in pencil hardness. [6] A method for forming an anti-glare hard coat layer, wherein the anti-glare hard coat layer having a concavo-convex shape on the surface has a ten-point average roughness Rz _JIS of 0.2 to 1.0 μm and an average length RSm of roughness curve elements of 5 ~100μm surface uneven shape. [7] A method for forming an antiglare hard coat layer, wherein the hard coat composition further contains light-transmitting fine particles with an average particle diameter of 0.5-10 μm, and the refractive index (Rf1) of the light-transmitting fine particles is equal to that of the hard coat The refractive index (Rf2) of the layer-forming resin component contained in the composition satisfies the following relationship: 0.01≦|Rf1-Rf2|≦0.23. [8] A method for forming an anti-glare hard coating, wherein the aforementioned anti-glare hard coating having a concavo-convex shape has an optical comb having five widths of 0.125 mm, 0.25 mm, 0.5 mm, 1.0 mm, and 2.0 mm. The surface concave-convex shape of the transmission image sharpness (%) sum value (%) in the range of 300~480. [9] A method for forming an anti-glare hard coat, which further comprises a step of forming a functional layer on the concave-convex surface of the obtained anti-glare hard coat after the peeling step, and the functional layer is selected from One or more of the group consisting of a refractive index layer, a low refractive index layer, and an antifouling layer. [10] A method for forming an antiglare hard coat layer, further comprising: a decorative layer forming step, which is to form a decorative layer on the other side of the transparent support substrate. [11] A method of manufacturing a display with an anti-glare hard coat, comprising the step of disposing an anti-glare hard coat on the surface of the display, and the anti-glare hard coat is obtained by the above method. [12] A method of manufacturing a display with an anti-glare hard coating, wherein the display is a touch panel display. Invention effect

According to the forming method of the present invention, it is possible to form an anti-glare hard coating having a rough surface shape capable of exhibiting good anti-glare performance and excellent scratch resistance.

form for carrying out the invention First, the course of arriving at the present invention will be described. The inventors of the present case have conducted a review on methods for improving the scratch resistance of the anti-glare layer. It is conceivable that as one of the means to improve the scratch resistance of the anti-glare layer, there may be, for example, a means of increasing the cross-linking density in order to increase the hardness of the coating. On the other hand, increasing the cross-linking density of the coating may affect the surface unevenness of the anti-glare layer. For example, a coating composition containing the first component and the second component is applied, and then the first component and the second component are separated to form a fine concave-convex shape. On the other hand, for such a coating composition containing the first component and the second component, when designing to increase the crosslink density of the obtained antiglare layer, the properties and phase separation conditions of the coating composition will change, and some Tendency to damage the fineness of concave-convex shape. Furthermore, when trying to form a finer concave-convex shape with the coating composition containing the first component and the second component, the crosslink density and coating film thickness tend to decrease, which has been clearly known through experiments. As mentioned above, especially when using a paint composition containing the first component and the second component, it has been one of the technical issues to improve the scratch resistance while forming a fine uneven shape.

The inventors of the present invention have examined a method of forming an anti-glare hard coat layer having fine unevenness (for example, by using a coating composition containing the first component and the second component) and having excellent scratch resistance. In the above-mentioned review, a method of using an anti-glare layer having a fine concave-convex shape as a template and transferring the concave-convex shape on the surface of the hard coat layer has been discussed. Then, it was found that by using the anti-glare layer with the surface of the fine concave-convex shape as a template, using a hard coating composition containing specific ingredients, and transferring the concave-convex shape to the hard coat layer through specific steps, it is possible to form a fine concave-convex shape and An anti-glare hard coating excellent in scratch resistance has finally completed the present invention. Hereinafter, the present invention is described in detail as follows.

The method for forming the anti-glare hard coat layer of the present invention is to provide an anti-glare hard coat layer with concave-convex shapes on at least one side of the transparent support substrate, comprising the following steps: A step of making a template base material, which produces a template base material with a concave-convex shape on the surface; A coating step of coating a hard coating composition on one side of the transparent support substrate to form an unhardened hard coating; The surface contact step, which makes the surface contact of the two substrates in the direction in which the concave-convex shape surface of the aforementioned template substrate is opposite to the surface of the aforementioned unhardened hard coating layer; a hardening step of hardening the unhardened hard coat layer by irradiating active energy rays; and A stripping step, which strips the template substrate from the hardened hard coat layer.

Formwork substrate production In this specification, "template substrate" means: having a concave-convex surface, and by making the concave-convex surface of the template substrate and the surface of the uncured hard coat layer obtained by coating the anti-glare hard coating composition face each other Direction surface contact to transfer the concave and convex shape, and form the substrate with concave and convex shape on the surface of the hard coat layer.

The concave-convex surface of the above-mentioned template base material can be formed by various methods for forming the concave-convex surface generally used in this technical field. As for the generally used method, for example, a coating composition containing fine particles with an average particle size of 0.1-5 μm can be applied and hardened to form a concave-convex surface due to the size of the fine particles. The aforementioned microparticles can be, for example, inorganic oxide particles such as silicon oxide (SiO ₂ ) particles, aluminum oxide particles, titanium oxide particles, tin oxide particles, antimony-doped tin oxide (abbreviated: ATO) particles, and zinc oxide particles; and , Polystyrene particles, melamine resin particles, acrylic particles, acrylic-styrene particles, polysiloxane particles, polycarbonate particles, polyethylene particles and polypropylene particles and other organic resin particles. Other methods include, for example, a method of forming a concave-convex surface by cutting the surface of the base material.

The concave-convex shape on the surface of the template base material is preferably a concave-convex shape formed by coating the concave-convex shape of the first component and the second component to form a paint composition, and separating the first component and the second component. The concave-convex shape obtained by separating the first component and the second component occurs naturally due to the configuration of the concave-convex, and an irregular concave-convex shape can be formed. Therefore, there is an advantage that no moiré occurs due to the regularity of the concavo-convex arrangement. Furthermore, forming a template substrate by coating a concave-convex shape-forming coating composition containing the first component and the second component on a transparent substrate has the advantage of forming a template substrate with high active energy ray transmittance. By using a template substrate with a high transmittance of active energy rays, there is an advantage that the uncured hard coat layer can be cured by irradiating active energy rays from the template substrate side in the hardening step described in detail below.

In the aforementioned concavo-convex shape forming paint composition, the combination of the first component and the second component that will cause phase separation can be exemplified: the SP value (SP ₁ ) of the first component and the SP value (SP ₂ ) of the second component will satisfy The form of the following conditions. SP ₂ <SP ₁ SP ₁ -SP ₂ ≧0.5 If the concave-convex shape forming coating composition containing the first component and the second component satisfying the above conditions is coated on the substrate, based on the SP of the first component and the second component Value difference, the first component and the second component will be separated, and a coating film with continuous random unevenness can be formed on the surface.

SP value is the abbreviation of solubility parameter (solubility parameter), which can be the standard of solubility. The larger the value of the SP value, the higher the polarity, and conversely, the smaller the value, the lower the polarity.

For example, the SP value can be measured by the following method [Reference: SUH, CLARKE, J.P.S.A-1, 5, 1671~1681(1967)].

烷、丙酮等 不良溶劑…正己烷、離子交換水等 濁點測定：使用50ml滴定管滴定不良溶劑，以發生混濁之點作為滴定量。Measurement temperature: 20°C Sample: Weigh 0.5g of resin into a 100ml beaker, add 10ml of good solvent with a quantitative pipette, and dissolve it with a magnetic stirrer. Solvent: Good solvent... 2

Poor solvents such as alkane, acetone... Determination of cloud point of n-hexane, ion-exchanged water, etc.: Use a 50ml burette to titrate the poor solvent, and take the point where turbidity occurs as the titration amount.

The SP value δ of the resin can be given by the following formula.

[數學式2]

[數學式3]

[mathematical formula 1]

[mathematical formula 2]

[mathematical formula 3]

Vi: molar volume of solvent (ml/mol) φi: Volume fraction of each solvent at the cloud point δi: SP value of solvent ml: low SP poor solvent mixed system mh: High SP poor solvent mixed system

The difference between the SP value of the first component and the SP value of the second component is preferably at least 0.5, more preferably at least 0.8. The upper limit of the difference in SP values is not particularly limited, but is generally 15 or less. When the difference between the SP value of the first component and the SP value of the second component is 0.5 or more, the compatibility between the components is low, and it is conceivable that the first component and the second component will be separated after coating the concave-convex shape forming coating composition. phase separation.

In this embodiment, it is preferable to contain an active energy ray-curing component as the first component. In addition, an unsaturated double bond-containing acrylic copolymer is preferably used as the second component.

Preferably, a monomer, oligomer or polymer having at least one unsaturated double bond group is included as the first component. Specific examples of these include: (meth)acrylate monomers having at least one unsaturated double bond group, (meth)acrylate oligomers, (meth)acrylate polymers, urethane Ester (meth)acrylate oligomers, urethane (meth)acrylate polymers and their modified monomers, oligomers or polymers, etc. The first component preferably contains polyfunctional (meth)acrylate monomers, polyfunctional (meth)acrylate oligomers, polyfunctional (meth)acrylate polymers, polyfunctional urethane (meth) ) acrylate monomers, multifunctional urethane (meth)acrylate oligomers, multifunctional urethane (meth)acrylate polymers and other multifunctional (meth)acrylate compounds and multifunctional amines At least one type of ethyl formate (meth)acrylate compound. By including such a compound, the crosslink density after hardening can be increased, and there is an advantage that the effect of improving the surface hardness can be further enhanced.

The first component more preferably contains a polyfunctional (meth)acrylate monomer. Specific examples of multifunctional (meth)acrylates include polypropylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, 1,3-adamantyldimethanol di(meth) Acrylates, trimethylolpropane tri(meth)acrylate, trimethylolpropane ethylene oxide modified tri(meth)acrylate, trimethylolpropane propylene oxide modified tri(meth)acrylate Acrylate, Isocyanuric acid ethylene oxide modified di(meth)acrylate, Isocyanuric acid ethylene oxide modified tri(meth)acrylate, Neopentylthritol tri(methyl) Acrylates, neopentylthritol tetra(meth)acrylate, dimethylolpropane tetra(meth)acrylate, diperythritol penta(meth)acrylate and diperythritol hexa(meth)acrylate ) acrylate, etc.

The above-mentioned (meth)acrylate monomer, (meth)acrylate oligomer, and urethane (meth)acrylate oligomer preferably have a weight average molecular weight of less than 5,000. For example, the (meth)acrylate monomer and urethane (meth)acrylate monomer preferably have a molecular weight above 70 and a weight average molecular weight of less than 3000, more preferably a molecular weight of above 70 and a weight average molecular weight of less than 2500. In addition, the weight average molecular weight of the (meth)acrylate oligomer and the urethane (meth)acrylate oligomer is preferably 100 or more and less than 5,000. In addition, the weight average molecular weight of the above-mentioned (meth)acrylate polymer and urethane (meth)acrylate polymer is preferably less than 50,000.

The second component includes, for example, an unsaturated double bond-containing acrylic copolymer, cellulose resin, and the like. Examples of acrylic copolymers containing unsaturated double bonds include: for resins obtained by copolymerizing (meth)acrylic monomers with other monomers having ethylenically unsaturated double bonds, (meth)acrylic monomers and Other resins formed by reacting monomers with ethylenically unsaturated double bonds and epoxy groups, resins formed by reacting (meth)acrylic monomers with other monomers having ethylenically unsaturated double bonds and isocyanate groups, etc. , the addition of acrylic acid or glycidyl methacrylate and other components with unsaturated double bonds and other functional groups. These unsaturated double bond-containing acrylic copolymers may be used alone or in combination of two or more. The weight average molecular weight of the unsaturated double bond-containing acrylic acid copolymer is preferably 3,000-100,000, more preferably 3,000-50,000.

The cellulose resin may, for example, be cellulose acetate butyrate or cellulose acetate propionate.

The mass ratio of the above-mentioned first component to the second component is preferably the first component: the second component = 98.5: 1.5 or even 55: 45, and is more preferably 98.5: 1.5 or even 60: 40, more preferably 98: 2 or even 70: 30.

The aforementioned concavo-convex shape-forming coating composition preferably contains a photopolymerization initiator. With the presence of a photopolymerization initiator, the resin component can be well polymerized by irradiating active energy rays such as ultraviolet rays. Examples of the photopolymerization initiator include alkylacetophenone-based photopolymerization initiators, acylphosphine oxide-based photopolymerization initiators, titanocene-based photopolymerization initiators, and oxime ester-based photopolymerization initiators. The preferred amount of the photopolymerization initiator is 0.01 to 20 parts by mass, more preferably 1 to 10 parts by mass, relative to 100 parts by mass of the resin component of the concave-convex shape forming paint composition. The said photoinitiator may be used individually, and may use it in combination of 2 or more types of photoinitiators.

The uneven surface shape is formed by coating the above-mentioned uneven shape forming coating composition on a base material and curing it. The coating method of the concave-convex shape forming coating composition can be selected in due course according to the conditions of the composition and the coating steps. For example, dip coating, air knife coating, curtain coating, roll coating, wire coating, etc. Coating is performed by a bar coating method, a die coating method, an inkjet method, a gravure coating method, or an extrusion coating method (US Pat. No. 2,681,294 specification). Various polymer substrates can be used as the substrate for coating the concave-convex shape forming paint composition. Substrate A transparent support substrate as described in detail below can be used.

By hardening the coating film obtained by applying the concave-convex shape forming coating composition, the first component and the second component contained in the composition are phase-separated, and a template base material having a concave-convex shape surface can be formed. This hardening can be performed by irradiation with a light source that emits active energy rays corresponding to the desired wavelength. The active energy rays to be irradiated can be, for example, light with a cumulative light intensity of 30 to 5000 mJ/cm ² . In addition, the wavelength of the irradiation light is not particularly limited, but for example, ultraviolet light having a wavelength of 360 nm or less can be used. Such light can be obtained using a high-pressure mercury lamp, an ultrahigh-pressure mercury lamp, or the like.

Transparent Support Substrate As the above-mentioned transparent supporting substrate provided with an anti-glare hard coat layer, various substrates used in this technical field can be used without particular limitation. Specific examples of the transparent support substrate include polycarbonate films, polyester films such as polyethylene terephthalate and polyethylene naphthalate, diacetyl cellulose and triacetyl cellulose Substrates made of transparent polymers such as cellulose-based films such as cellulose and acrylic films such as polymethyl methacrylate. In addition, other examples of transparent support substrates can also be mentioned: polystyrene and acrylonitrile-styrene copolymers and other styrene-based films; polyvinyl chloride, polyethylene, polypropylene, cyclic or even norbornene structures Olefin-based films such as polyolefins and ethylene-propylene copolymers; substrates made of transparent polymers such as amide-based films such as nylon and aromatic polyamides. In addition, examples of the transparent support substrate include polyimide, polypolyethylene, polyethersulfone, polyetheretherketone, polyphenylene sulfide, polyvinyl alcohol, polyvinylidene chloride, and polyvinyl butyral. , polyarylate, polyoxymethylene, epoxy resin, and blends of the above polymers, etc., are substrates made of transparent polymers.

Furthermore, the above-mentioned transparent supporting substrate may be a laminated multi-substrate composed of transparent polymers. For example, it may be a laminate of a film made of an acrylic resin and a film made of a polycarbonate resin, or a laminate of a sheet.

The above-mentioned transparent support substrate can be appropriately selected from among these transparent polymer substrates depending on the application, one with less optical birefringence or one whose phase difference has been controlled to 1/4 (λ/4) of the wavelength (for example, 550nm) or 1 of the wavelength /2(λ/2), and even those who do not control birefringence at all.

The thickness of the transparent support base material can be appropriately selected depending on its application and member processing method. In general, from the standpoint of workability such as strength and handling properties, it is about 10 to 5000 μm, especially 20 to 3000 μm, and more preferably 30 to 3000 μm.

Painting steps The coating step is to apply a hard coating composition on at least one side of the above-mentioned transparent support substrate to form an uncured hard coating layer.

Hard coating composition The hard coating composition used in the coating step includes polymerizable unsaturated group-containing oligomers or polymers with a weight average molecular weight in the range of 1,000 to 200,000. The above polymerizable unsaturated group-containing oligomer or polymer is a layer-forming resin component of the hard coat layer.

The above method includes the step of bringing the template substrate into surface contact with the unhardened hard coat layer obtained by applying the hard coat composition. Therefore, even if the stencil substrate is brought into surface contact with the hard coat composition in an uncured state, the resulting hard coat must maintain the form of the layer. In this method, the layer-forming resin component containing a polymerizable unsaturated group-containing oligomer or polymer having a weight-average molecular weight in the range of 1,000 to 200,000 as a hard coat layer has a surface that can perform well as described below. Advantages of the contact step.

The above-mentioned oligomers or polymers containing polymerizable unsaturated groups are oligomers or polymers having a weight average molecular weight in the range of 1,000 to 200,000 and having polymerizable unsaturated groups. The above polymerizable unsaturated group-containing oligomer or polymer preferably has one or more polymerizable unsaturated groups selected from the group consisting of acryl groups and methacryl groups.

Specific examples of the above-mentioned oligomers or polymers containing polymerizable unsaturated groups include, for example: urethane (meth)acrylate oligomers or polymers with a weight average molecular weight in the range of 1,000 to 200,000, weight average Acryl (meth)acrylate oligomers or polymers with a molecular weight in the range of 1,000 to 200,000.

The above-mentioned urethane (meth)acrylate oligomer or polymer can be prepared by methods such as the following: (1) Addition reaction of a compound with a hydroxyl group and an acryl group (or methacryl group) to a polyisocyanate compound with a terminal isocyanate group in the molecule; and (2) Reacting isocyanate group-containing (meth)acrylate monomers to react polyurethane polyols obtained by reacting polyisocyanate compounds with polyols.

The above-mentioned polyisocyanate compounds can be exemplified as: 2,4-mylene diisocyanate, 2,6-mylene diisocyanate, 1,3-xylene diisocyanate, 1,4-xylene diisocyanate, stubble phenylene diisocyanate, 1,5-naphthalene diisocyanate, m-phenylene diisocyanate, p-phenylene diisocyanate, diphenylmethane diisocyanate, 4,4'-diphenylmethane diisocyanate, 4,4'- Dibenzyl diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, dicyclohexylmethane diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4-tri Methylhexamethylene diisocyanate or diisocyanate compounds obtained by hydrogenating aromatic isocyanates among these diisocyanate compounds (such as hydrogenated stubble diisocyanate, hydrogenated diphenylmethane diisocyanate and other diisocyanates) Compounds), triphenylmethane triisocyanate, dimethylene triphenyl triisocyanate and other divalent or trivalent polyisocyanate compounds, as well as biuret-type adducts and isocyanate cyclo-adducts of these diisocyanates Wait.

Among the above (1), the compound having hydroxyl group and acryl group (or methacryl group) can be exemplified: neopentylthritol tri(meth)acrylate, dipenteoerythritol penta(meth)acrylate , 2-hydroxyethyl (meth)acrylate, glycerol di(meth)acrylate and the addition of ethylene oxide, propylene oxide, ε-caprolactone and γ-butyrolactone, etc. The resulting alkylene oxide modified or lactone modified compound and the like.

Examples of the polyhydric alcohols in (2) above include: ethylene glycol, propylene glycol, butylene glycol, neopentyl glycol, 1,6-hexanediol, trimethylolpropane, glycerin, neopentyl glycol, polycaprolactone Ester diol, polyester polyol and polyether polyol, etc.

The (meth)acrylate monomers containing isocyanate groups in (2) above include, for example: ethyl isocyanate acrylate, propyl isocyanate acrylate, and the addition of hexamethylene to active hydrogen-containing polymerizable monomers such as hydroxyethyl acrylate. Unsaturated compounds composed of polyisocyanate compounds such as diisocyanate.

The aforementioned urethane (meth)acrylate oligomer or polymer may also be a urethane urea (meth)acrylate oligomer or polymer having a urea bond. For example, a urethane urea (meth)acrylate oligomer or polymer can be prepared by using polyamine in addition to the polyol of (2) above.

The above-mentioned acryl (meth)acrylate oligomer or polymer is an acrylic oligomer or polymer containing acryl and/or methacryl. Specifically, for example: the compound obtained by adding (meth)acrylic acid to the acrylic resin obtained by the copolymerization of glycidyl methacrylate; Compounds of hydroxyethyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, neopentylthritol tri(meth)acrylate, etc., acrylic resins obtained by copolymerization of hydroxyl-containing monomers Resin made by adding 2-acryloxyethyl isocyanate, etc. These may be used individually or in combination of 2 or more types.

Among the above-mentioned urethane (meth)acrylate oligomers or polymers and acrylic acid (meth)acrylate oligomers or polymers, those having a weight average molecular weight of 1,000 to 200,000 can be used. For the above-mentioned polymerizable unsaturated group-containing oligomer or polymer, one or more functional groups selected from the group consisting of acryl and methacryl groups have 2 or more functional groups is appropriate, more preferably 3 or more, and more preferably 5 or more.

A commercial item can be used for the said polymerizable unsaturated group containing oligomer or polymer. For example, commercially available urethane (meth)acrylate oligomers or polymers described above can be used: Nippon Kayakusha DPHA-40H, UX-5000, UX-5102D20, UX-5103D, UX-5005, UX-3204, UX-4101, UXT-6100, UX-6101, UX-8101, UX-0937, UXF -4001-M35, UXF-4002; UF-8001G, UA-510H made by Gongrongsha Chemical Society; DAICEL-ALLNEX LTD.製EBECRYL 244、EBECRYL 284、EBECRYL 8402、EBECRYL 8807、EBECRYL 264、EBECRYL 265、EBECRYL 9260、EBECRYL 8701、EBECRYL 8405、EBECRYL 1290、EBECRYL 5129、EBECRYL 220、KRM 8200、KRM 7804、KRM 8452 ; UV-1600B, UV-1700B, UV-6300B, UV-7600B, UV-7640B, UV-7461B, UV-7650B, UV-3520EA, UV-6640B, Ziguang UV-7000B, Ziguang UV-305F; CN-9001, CN-9004, CN-9005, CN-965, CN-9178, CN-9893, CN-9782, CN-964, CN-9013, CN-9010 manufactured by ARKEMA; U-10PA, U-10HA, UA-33A, UA-53H, UA-32P, U-15HA, UA-122P, UA-160TM, UA-31F, UA-7100, UA-4200, UA manufactured by Shin-Nakamura Chemical Co., Ltd. -4400; and Negami Industry Co., Ltd. Art Resin UN-3320HA, Art Resin UN-3320HB, Art Resin UN-3320HC, Art Resin UN-3320HS, Art Resin UN-904, Art Resin UN-901T, Art Resin UN-905, Art Resin UN- 951, Art Resin UN-952, Art Resin UN-953, Art Resin UN-954, Art Resin UN-906, Art Resin UN-906S, Art Resin UN-907, Art Resin UN-908, Art Resin UN-333, Art Resin UN-5507, Art Resin UN-6300, Art Resin UN-6301, Art Resin UN-7600, Art Resin UN-7700, Art Resin UN-9000PEP, Art Resin UN-9200, Art Resin UN-904UREA, Art Resin UN-H7UREA et al.

For example, commercially available acrylic (meth)acrylate oligomers or polymers described above can be used: UNIDIC V-6840, UNIDIC V-6841, UNIDIC V-6850, UNIDIC EMS-635, UNIDIC WHV-649 manufactured by DIC Co., Ltd.; Hitaloid 7975, Hitaloid 7977, Hitaloid 7988, Hitaloid 7975D manufactured by Hitachi Chemical Co., Ltd.; and Art Cure RA-3969MP, Art Cure RA-3960PG, Art Cure RA-3602MI, Art Cure OAP-5000, Art Cure OAP-2511, Art Cure AHC-9202MI80, Art Cure RA-3704MB, Art Cure RA- 3953MP, Art Cure RA-4101, Art Cure MAP-4000, Art Cure MAP2801, etc.

The above polymerizable unsaturated group-containing oligomers or polymers may be used alone or in combination of two or more.

The above-mentioned hard coating composition has the following advantages by including the above-mentioned polymerizable unsaturated group-containing oligomer or polymer with a weight average molecular weight in the range of 1,000 to 200,000: in the surface contact step described below, it can be maintained without While the thickness of the hardened hard coat layer is increased, the concave and convex shapes on the surface of the template substrate can be well transferred to the unhardened hard coat layer. Furthermore, since it contains a polymerizable unsaturated group, it has the advantages of good scratch resistance and chemical resistance after curing, and no bad appearance due to bleeding after evaluation of moisture and heat resistance, heat resistance, light resistance, etc.

The said hard-coat composition may further contain a polymerizable unsaturated group containing monomer as needed. The polymerizable unsaturated group-containing monomer is the layer-forming resin component of the hard coat layer as well as the above-mentioned polymerizable unsaturated group-containing polymer. The condition for the polymerizable unsaturated group-containing monomer is that the polymerizable unsaturated group equivalent weight is 90 to 500 g/eq.

The above hard coating composition has the advantage of improving the scratch resistance of the obtained anti-glare hard coating by further comprising a polymerizable unsaturated group-containing monomer. Furthermore, due to the adjustment of the viscosity, it has the advantages of improving the coating workability and adjusting the peel strength after lamination within an appropriate range.

烷二醇二(甲基)丙烯酸酯、乙氧基化(2)雙酚A二(甲基)丙烯酸酯、乙氧基化(3)雙酚A二(甲基)丙烯酸酯、乙氧基化(4)雙酚A二(甲基)丙烯酸酯、乙氧基化(10)雙酚A二(甲基)丙烯酸酯、丙氧基化(3)雙酚A二(甲基)丙烯酸酯、三環癸烷二甲醇二(甲基)丙烯酸酯、9,9-雙[4-(2-羥乙氧基)苯基]茀二(甲基)丙烯酸酯等2官能(甲基)丙烯酸酯單體； 甘油三(甲基)丙烯酸酯、三羥甲基丙烷三(甲基)丙烯酸酯、乙氧基化(3)三羥甲基丙烷三丙烯酸酯、乙氧基化(6)三羥甲基丙烷三丙烯酸酯、乙氧基化(9)三羥甲基丙烷三丙烯酸酯、丙氧基化(3)三羥甲基丙烷三丙烯酸酯、丙氧基化(6)三羥甲基丙烷三丙烯酸酯、丙氧基化(9)三羥甲基丙烷三丙烯酸酯、新戊四醇三(甲基)丙烯酸酯、乙氧基化(4)新戊四醇三(甲基)丙烯酸酯、乙氧基化(8)新戊四醇三(甲基)丙烯酸酯、三(2-羥乙基)三聚異氰酸酯三(甲基)丙烯酸酯、己內酯改質(1)參(2-羥乙基)三聚異氰酸酯三(甲基)丙烯酸酯、己內酯改質(3)參(2-羥乙基)三聚異氰酸酯三(甲基)丙烯酸酯等3官能(甲基)丙烯酸酯單體； 新戊四醇四(甲基)丙烯酸酯、二新戊四醇四(甲基)丙烯酸酯、三新戊四醇四(甲基)丙烯酸酯、二三羥甲基丙烷四(甲基)丙烯酸酯、乙氧基化(4)新戊四醇四(甲基)丙烯酸酯、乙氧基化(8)新戊四醇四(甲基)丙烯酸酯等4官能(甲基)丙烯酸酯單體； 二新戊四醇五(甲基)丙烯酸酯、三新戊四醇五(甲基)丙烯酸酯等5官能(甲基)丙烯酸酯單體； 二新戊四醇六(甲基)丙烯酸酯、三新戊四醇六(甲基)丙烯酸酯等6官能(甲基)丙烯酸酯單體；及 三新戊四醇七(甲基)丙烯酸酯、三新戊四醇八(甲基)丙烯酸酯等7官能以上之(甲基)丙烯酸酯單體等。The above-mentioned polymerizable unsaturated group-containing monomer may, for example, be a polyfunctional (meth)acrylate monomer and have a polymerizable unsaturated group equivalent of 90 to 500 g/eq. A polyfunctional (meth)acrylate monomer can be prepared by dealcoholating a polyhydric alcohol and (meth)acrylate. Specific examples of polyfunctional (meth)acrylate monomers with a polymerizable unsaturated group equivalent of 90 to 500 g/eq include: ethylene glycol di(meth)acrylate, 1,6-hexanediol di( Meth)acrylate, polyethylene glycol (200) di(meth)acrylate, allyl (meth)acrylate, 1,4-butanediol di(meth)acrylate, neopentyl glycol di (meth)acrylate, di

Alkanediol Di(meth)acrylate, Ethoxylated (2) Bisphenol A Di(meth)acrylate, Ethoxylated (3) Bisphenol A Di(meth)acrylate, Ethoxylated (4) Bisphenol A di(meth)acrylate, Ethoxylated (10) Bisphenol A di(meth)acrylate, Propoxylated (3) Bisphenol A di(meth)acrylate , tricyclodecane dimethanol di(meth)acrylate, 9,9-bis[4-(2-hydroxyethoxy)phenyl] fennel di(meth)acrylate and other bifunctional (meth)acrylic acid ester monomers; glycerol tri(meth)acrylate, trimethylolpropane tri(meth)acrylate, ethoxylated (3) trimethylolpropane triacrylate, ethoxylated (6) trimethylolpropane Methylolpropane Triacrylate, Ethoxylated (9) Trimethylolpropane Triacrylate, Propoxylated (3) Trimethylolpropane Triacrylate, Propoxylated (6) Trimethylolpropane propane triacrylate, propoxylated (9) trimethylol propane triacrylate, neopentylthritol tri(meth)acrylate, ethoxylated (4) neopentylthritol tri(meth) Acrylates, Ethoxylated (8) Neopentylthritol Tri(meth)acrylate, Tris(2-Hydroxyethyl) Trimeric Isocyanate Tri(meth)acrylate, Caprolactone modified (1) (2-hydroxyethyl) isocyanate tri(meth)acrylate, caprolactone modified (3) ginseng (2-hydroxyethyl) isocyanate tri(meth)acrylate and other 3 functional (methyl) ) Acrylic ester monomer; Tetra(meth)acrylate, ethoxylated (4) neopentylthritol tetra(meth)acrylate, ethoxylated (8) neopentylthritol tetra(meth)acrylate etc. base) acrylate monomers; 5-functional (meth)acrylate monomers such as dipenteopentylthritol penta(meth)acrylate and trineopentylthritol penta(meth)acrylate; Hexafunctional (meth)acrylate monomers such as (meth)acrylate and trineopentylthritol hexa(meth)acrylate; Octa(meth)acrylate and other seven or more functional (meth)acrylate monomers, etc.

These polyfunctional (meth)acrylate monomers may be used individually by 1 type, and may mix and use 2 or more types.

The hard coat composition comprises the polymerizable unsaturated group-containing oligomer or polymer with a weight average molecular weight in the range of 1,000 to 200,000, and the polymerizable unsaturated group-containing polymerizable unsaturated group equivalent weight of 90 to 500 g/eq. In the case of a base monomer, the amount of the above-mentioned polymerizable unsaturated group-containing oligomer or polymer is preferably 15 to 85 parts by mass relative to 100 parts by mass of the solid content of the layer-forming resin component contained in the above-mentioned hard coat composition, The amount of the polymerizable unsaturated group-containing monomer is preferably 85 to 15 parts by mass. By satisfying the above-mentioned quality range, the obtained anti-glare hard coating has the advantages of good uneven shape transfer rate, scratch resistance, and chemical resistance.

The hard-coat composition may further include light-transmitting fine particles with an average particle diameter in the range of 0.5 to 10 μm as needed. By including light-transmitting fine particles with an average particle diameter in the range of 0.5 to 10 μm in the hard coating composition, it has the advantages of suppressing the glare of the obtained anti-glare hard coating and increasing the hardness. The above-mentioned average particle size is more preferably in the range of 1.0 to 10 μm.

In addition, the so-called glare refers to the phenomenon that the intensity of brightness occurs in the coating. Display devices such as monitors display images by emitting light from inside. Here, the light emitted from the inside of the display device is dependent on the concave-convex state of the coating to change the light-incident state, and the light entering the concave-convex state may cause light intensity constriction when the light is emitted. The amount of light constriction incurs luminosity intensities, which will be recognized as glare. This glare has a problem of causing eye fatigue to a person viewing the display device.

"Translucent microparticles" in this specification means transparent or translucent microparticles with an average light transmittance of 30% or more for visible light. In addition, the average particle diameter of the above-mentioned translucent fine particles is a value of D50. In this specification, D50 means: the particle size measured by a laser diffraction particle size distribution meter, and the converted volume accumulation reaches 50%.

The light-transmitting fine particles are preferably those that satisfy the following relationship between the refractive index (Rf1) of the light-transmitting fine particles and the refractive index (Rf2) of the layer-forming resin component contained in the hard coat composition. 0.01≦｜Rf1―Rf2｜≦0.23 By making the refractive index (Rf1) of the light-transmitting fine particles and the refractive index (Rf2) of the layer-forming resin component contained in the hard coat composition satisfy the above relationship, the antiglare performance of the obtained antiglare hard coat layer can be improved. The advantage of good anti-glare performance.

The refractive index (Rf1) of the light-transmitting fine particles and the refractive index (Rf2) of the layer-forming resin component contained in the hard coat composition can be measured using, for example, an Abbe's refractometer.

The light-transmitting fine particles with an average particle diameter in the range of 0.5-10 μm can use organic or inorganic fine particles within the above-mentioned average particle diameter range. Commercially available translucent fine particles with an average particle diameter in the range of 0.5 to 10 μm can be used. Commercially available products include, for example, Techpolymer SSX series (styrene-acrylic copolymer fine particles) manufactured by Sekisui Chemical Co., Ltd., Chemisnow SX series (styrene polymer fine particles) manufactured by Soken Chemical Co., Ltd., Chemisnow MX series (acrylic polymer fine particles) Fine particles), SEAHOSTAR KE-P, KE-S series (silicon oxide fine particles) manufactured by Nippon Shokubai Co., Ltd., SOLIOSTAR RA (polysiloxane-acrylic acid copolymer fine particles), EPOSTAR S12 (melamine polymer fine particles), EPOSTAR MA series (styrene-acrylic copolymer fine particles), acrylic copolymer fine particles, MSP series manufactured by NIKKO RICA CORPORATION, NH series (polysiloxane fine particles), AZ series manufactured by NIPPON STEEL & SUMIKIN MATERIALS CO.,LTD., AY series (alumina microparticles), etc. The aforementioned Techpolymer SSX series (styrene-acrylic copolymer fine particles), Chemisnow SX series (styrene polymer fine particles), and EPOSTAR MA series (styrene acrylic copolymer fine particles) have a suitable refractive index (Rf1) satisfying the above relationship and From the viewpoint of excellent dispersibility, it is more desirable.

other ingredients The above-mentioned hard coat composition preferably contains a photopolymerization initiator. By the presence of a photopolymerization initiator, active energy rays such as ultraviolet rays can be irradiated to make the resin component polymerize well. As an example of a photopolymerization initiator, the photopolymerization initiator mentioned above can be suitably used. The preferable quantity of a photoinitiator is 0.01-20 mass parts with respect to 100 mass parts of resin components of a hard-coat composition, More preferably, it is 1-10 mass parts. The photopolymerization initiator may be used alone, and may be used in combination of two or more kinds of photopolymerization initiators.

Various additives can be added to the said hard-coat composition as needed. Examples of such additives include common additives such as polymerization initiators, antistatic agents, plasticizers, surfactants, antioxidants, ultraviolet absorbers, surface regulators, and leveling agents.

For example, microparticles with an average particle size of less than 0.5 μm can be used for other components. Such fine particles include, for example, translucent fine particles having an average particle diameter D50 of 5 nm or more and less than 500 nm. The light-transmitting fine particles with an average particle diameter D50 of 5 nm or more and less than 500 nm can be, for example, nanometer-level organic or inorganic fine particles. Colloidal silica is preferably used for light-transmitting fine particles. Colloidal silicon oxide can be reactive colloidal silicon oxide that introduces reactive groups such as (meth)acryl groups on the surface of silicon oxide particles through surface modification, things that do not have reactive groups on the surface of silicon oxide particles, or non-reactive Non-reactive colloidal silica for organic-based surface modification.

The above-mentioned hard coating composition can be prepared by the methods commonly used by people in the industry. For example, it can be prepared by mixing the above-mentioned components using a commonly used mixing device such as a paint shaker, mixer, or spreader.

Coating of hard coating composition In the coating step, the above-mentioned hard coat composition is coated on at least one side of the transparent support substrate to form an uncured hard coat layer. The coating of the hard coating composition can be selected in due time depending on the properties of the hard coating composition and the conditions of the coating steps. For example, it can be dip coating, air knife coating, curtain coating, roll coating, wire bar Coating is carried out by coating method, die coating method, inkjet method, gravure coating method or extrusion coating method (US Patent No. 2681294 specification).

As for the coating of the above-mentioned hard coating composition, it is preferable to apply so that the film thickness of the uncured hard coating is within the range of 0.5-20 μm, and it is more preferable to apply such that the film thickness is within the range of 1-15 μm. By making the film thickness within the above-mentioned range, there is an advantage that the shock resistance, heat resistance, curl resistance, crack resistance, scratch resistance and hardness of the obtained anti-glare hard coating can be designed within a good range.

surface contact step The surface contact step is to make surface contact in a direction opposite to the surface of the hard coat layer by making the concave-convex shape of the template base material face the unhardened hard coat layer formed in the above coating step. Thereby, the surface shape of the unhardened hard coat layer will be transformed into the concave-convex shape of the surface of the template base material which is in contact with it, and the concave-convex shape of the template base material surface will be transferred on the surface of the unhardened hard coat layer.

In the step of contacting the concave-convex shape surface of the template base material with the unhardened hard coating surface, the pressing pressure is in the range of 0.001~25MPa. The above pressure should be in the range of 0.001~5MPa, more preferably in the range of 0.005~5MPa. By making the pressing pressure within the above range, the concave and convex shape of the template substrate can be well transferred to the uncured hard coat layer, and in addition, it is possible to prevent the occurrence of unevenness between the concave and convex surface of the template substrate and the uncured hard coat layer. Voids, substrate deformation, uneven film thickness, and coating film extrusion from the end.

The peeling strength of the contact portion between the concave-convex surface of the template base material and the unhardened hard coating surface should preferably be in the range of 0.01-2N/25mm. By making the peeling strength of the surface contact portion of the hard coat surface unhardened within the above range, the floating of the template base material and the uncured hard coat layer will be suppressed, and the concave-convex shape of the template base material can be well transformed. Advantages of printing on unhardened hard coats. In addition, shape transfer defects caused by poor surface contact are suppressed, and there are also advantages of improving productivity and improving workability.

The method of adjusting the peeling strength of the contact portion between the concave-convex shape surface of the template substrate and the uncured hard-coat surface within the above-mentioned range includes, for example, a method of using a hard-coat composition containing : polymerizable unsaturated group-containing oligomers or polymers with a weight average molecular weight in the range of 1,000 to 200,000; and polymerizable unsaturated group-containing monomers with a polymerizable unsaturated group equivalent weight of 90 to 500 g/eq.

hardening step In the hardening step, active energy rays are irradiated with the concave-convex surface of the template substrate and the surface of the uncured hard coat layer in contact with each other to harden the uncured hard coat coat layer. Irradiation of active energy rays can be performed from the side of the transparent support substrate provided with an uncured hard coat layer. In addition, when the template substrate is light-transmitting, the active energy rays can also be irradiated from the side of the template substrate.

Irradiation of active energy rays can be carried out by irradiating with a light source (which emits active energy rays corresponding to a desired wavelength). The active energy rays to be irradiated can use, for example, light with a cumulative light intensity of 15 to 5000 mJ/cm ² . In addition, the wavelength of the irradiated light is not particularly limited, but for example, ultraviolet light having a wavelength of 360 nm or less can be used. Such light can be obtained using a high-pressure mercury lamp, an ultrahigh-pressure mercury lamp, or the like.

Stripping step The stripping step is to strip the template substrate from the hard coat layer that has been hardened in the above hardening step. By peeling off the template substrate after the hard coat is hardened, there is an advantage that a denser concave-convex shape can be provided on the hard coat.

Anti-glare hard coating In the above method, after the active energy ray is irradiated, the peeling strength of the contact portion between the concave-convex shape surface of the template base material and the surface of the hard coat layer should be in the range of 0.005~1.5N/25mm. By making the peeling strength of the surface-contact portion of the cured hard coat layer and the template base material fall within the above range, there is an advantage that the template base material can be peeled off without destroying the concave-convex shape formed on the surface of the hard coat layer.

In addition, in the step of contacting the concave-convex shape surface of the template substrate with the unhardened hard coating surface in the above method, the transfer rate of the concave-convex shape is preferably 75-100% when the pressing pressure is 0.001-5 MPa. In the step of contacting the concave-convex surface of the stencil base material with the surface of the uncured hard coat layer, when the pressing pressure is 0.001~5MPa, the layer thickness of the uncured hard coat layer can be brought into contact without greatly damaging the thickness of the uncured hard coat layer. Also, as mentioned above, in the above method, when the pressing pressure is 0.001~5MPa, it is preferable that the uneven shape of the surface of the template substrate can be well transferred to the surface of the hard coat layer. The shape transfer rate is transferred within the range of 75~100%.

In this specification, the concavo-convex shape transfer rate can be obtained in the following order of steps. Measure the Rz _JIS (A) value of the template substrate. Press the concave-convex surface of the template substrate against the uncured hard-coated surface under a pressing pressure range of 0.001-5 MPa to bring them into surface contact. The uncured hard coat is cured by irradiating active energy rays while the template substrates are in surface-to-face contact. The template substrate was peeled off from the obtained hard coat layer, and Rz _JIS (B) of the formed concave-convex shape surface was measured. Using Rz _JIS (A) of the template base material and Rz _JIS (B) of the formed uneven surface, the uneven shape transfer rate can be obtained from the following formula (B)/(A)×100(%).

The pencil hardness of the antiglare hard coating is preferably 2H or above. Pencil hardness can be measured in accordance with JIS K 5600-5-4. By setting the pencil hardness of the antiglare hard coat layer to 2H or more, the hardness of the antiglare hard coat layer is high enough to be judged to have sufficient scratch resistance. The above-mentioned anti-glare hard coat is characterized in that it has a fine concave-convex shape and that the hardness of the hard coat is as high as a pencil hardness of 2H or more. The pencil hardness of the anti-glare hard coating is more preferably 3H or above.

The ten-point average roughness Rz _JIS of the uneven shape of the anti-glare hard coating surface is preferably 0.2 to 1.0 μm. Here, "10-point average roughness Rz _JIS " is one of the parameters indicating surface unevenness shape (roughness shape) stipulated in JIS B0601; 2001 Attachment JA. Ten-point average roughness Rz _JIS : the average from the highest peak (convex) to the fifth peak (from high to low) in the roughness curve of the reference length obtained by applying the cut-off value phase compensation band-pass filter The sum of the height and the average valley depth from the deepest valley bottom (recess) to the fifth valley (from deep to shallow). For example, the ten-point average roughness Rz _JIS can be obtained using a laser microscope in accordance with JIS B0601; 2001.

In addition, it is preferable that the average length RSm of the roughness curve element of the surface unevenness shape of the above-mentioned anti-glare hard coating is 5-100 μm. Here, the "average length RSm of the roughness curve element" is one of the parameters indicating the size and distribution of surface unevenness (roughness shape) specified in JIS B0601;2001. The average length RSm of the thickness curve element means the average length of the profile curve (thickness curve) element in the reference length. For example, the average length RSm of the roughness curve element can be obtained using a laser microscope (manufactured by VK-8700 KEYENCE, etc.) in accordance with JIS B0601; 2001.

The above-mentioned anti-glare hard coating is measured in the transmission image clarity test stipulated in JIS K 7374 (2007). The sum Tc(%) of the transmitted image sharpness Cn(%) is preferably 300 or more. The total value Tc(%) is more preferably in the range of 300~480.

The test for measuring the clarity of the transmitted image is to measure the light quantity of the transmitted light of the anti-glare hard coating through an optical comb of width n (mm) which is perpendicular to the optical axis of the transmitted light and moves at a speed of 10mm/min. Specifically, it measures using an image quality measuring device (manufactured by Suga Test Instruments Co., Ltd.). The image quality measuring device is composed of the following devices: an optical device, which uses the light transmitted through the slit as parallel light rays, and makes the light incident vertically on the anti-glare hard coating from the opposite side of the concave-convex surface of the anti-glare hard coating , and then detect through the optical comb moving on the transmitted light; and, a measurement system device, which records the measured light quantity variation as a waveform. The width ratio of the light part and the dark part in the optical comb is 1:1, and the width n (mm) is 0.125, 0.25, 0.5, 1, 2, etc., and the moving speed is 10mm/min.

In the measurement test of the clarity of the transmitted image, the maximum amount of transmitted light when there is a transmission part of the optical comb (bright place) on the optical axis is Mn, and the minimum amount of transmitted light is when there is a light-shielding part of the optical comb (dark place) on the optical axis The value is mn, and the transmission image clarity Cn (%) at this time is calculated by the following formula. Cn={(Mn-mn)/(Mn+mn)}×100

When the width n(mm) of the optical comb is 0.125, 0.25, 0.5, 1 and 2 respectively, the total value Tc(%) is 5 transmission image clarity C0.125(%), C0.25(%), C0. 5(%), the sum of C1(%) and C2(%), so the maximum value that can be taken is 500%.

The above-mentioned total value Tc (%) of the anti-glare hard coating is more than 300, which means that the anti-glare hard coating has high image clarity and image quality while having anti-glare performance. Due to the high image clarity of the anti-glare hard coating, it has the advantage of exerting the anti-glare effect without greatly reducing the image clarity of such as a high-resolution display.

The brightness and glare deviation of the above-mentioned anti-glare hard coating on a 326ppi display should be less than 2.6%. The above deviation can be obtained by measuring the brightness value glare at a distance of 500mm by using the I16 machine made by RADIANT and using a 326ppi display. The calculation of the deviation can be obtained by numerically analyzing the brightness value obtained above by using the software TrueTest. If the above deviation of the anti-glare hard coating is less than 2.6%, the occurrence of glare that reduces the visibility of the screen can be reduced, and the visibility can be judged to be good.

By forming the anti-glare hard coating by the above-mentioned method, it is possible to form an anti-glare hard coating having fine unevenness on the surface, high hardness, and excellent scratch resistance.

functional layer After the above peeling step, a functional layer can be further provided on the concave-convex surface of the obtained anti-glare hard coat layer if necessary. The functional layer can be, for example, a high-refractive-index layer, a low-refractive-index layer, a composite layer including a low-refractive-index layer and a high-refractive-index layer, and an antifouling layer. These functional layers can be formed by methods generally used in this technical field, such as coating and hardening the coating composition for functional layer formation.

decorative layer A decorative layer may be formed on the transparent support substrate on which the anti-glare hard coat layer has been formed, if necessary. For example, the above-mentioned anti-glare hard coating can be provided on one side of the transparent support substrate and a decorative layer can be provided on the other surface of the transparent support substrate. By providing a decorative layer, it can be used as a laminated member for molding and decoration.

When the decorative layer is provided, after the anti-glare hard coating is provided on one side of the transparent supporting substrate, the decorative layer can be provided on the other side of the transparent supporting substrate. In addition, when the active energy ray transmittance of the decorative layer is high, or when the active energy ray transmittance of the template substrate is high, the decorative layer may be provided on the other surface of the transparent support substrate in advance, and then the above-mentioned Anti-glare hard coat.

The above-mentioned decorative layer is a layer to which decorations such as patterns, characters, or metallic luster are applied. Such a decorative layer may, for example, be a printed layer or a vapor-deposited layer. Both of the printed layer and the vapor-deposited layer are layers for giving decoration. In the present invention, only one of the printed layer and the vapor-deposited layer may be provided as the decorative layer, or both the printed layer and the vapor-deposited layer may be provided. In addition, the printing layer may be a layer composed of a plurality of layers. From the viewpoint of easiness of working steps, etc., the above-mentioned decorative layer is preferably a printing layer.

The printing layer is a thing for decorating the surface of a molded body with patterns and/or characters. The printing layer can be, for example, a design composed of wood grain, stone grain, cloth grain, sand grain, geometric pattern, characters, and overall coloring. The printing layer material can use colored ink, which contains polyethylene resin such as vinyl chloride/vinyl acetate copolymer, polyamide resin, polyester resin, polyacrylic resin, polyurethane resin, etc. Ester resin, polyvinyl acetal resin, polyester urethane resin, cellulose ester resin, alkyd resin, chlorinated olefin resin and other resins are used as binders, and appropriate colored pigments or dyes are used as binders. Colorant. As the ink pigment used for the printing layer, the following ones can be used. In general, pigments can be used: azo-based pigments such as polyazo for yellow pigments, organic pigments such as isoindolinone, or inorganic pigments such as titanium nickel antimony oxides; azo pigments such as polyazo for red pigments. Nitrogen pigments, organic pigments such as quinacridone or inorganic pigments such as iron red; organic pigments such as phthalocyanine or inorganic pigments such as cobalt blue used as blue pigments; organic pigments such as aniline black used as black pigments; used as white pigments Titanium dioxide and other inorganic pigments.

As the ink dye used for the printing layer, various known dyes can be used within the range not impairing the effects of the present invention. In addition, as the printing method of the ink, conventional printing methods such as lithography, gravure printing, and screen printing, or conventional coating methods such as roll coating and spray coating may be used. At this time, instead of using a low-molecular-weight cross-linking compound as in the present invention, when a photocurable resin composition with a structure in which polymers are cross-linked is used, the surface has no stickiness, less interference during printing, and high productivity. good.

The evaporated layer can use at least one metal selected from the group consisting of aluminum, nickel, gold, platinum, chromium, iron, copper, indium, tin, silver, titanium, lead and zinc, alloys or compounds thereof, And it is formed by methods such as vacuum evaporation method, sputtering method, ion plating method, gold plating method and the like.

In order to obtain the desired surface appearance of the molded body, the thickness of the printed layer or evaporated layer used for decoration can be appropriately selected according to the degree of stretching during molding by the usual method.

monitor A transparent support substrate having an anti-glare hard coat layer provided by the above-mentioned method can be suitably used as a member arranged in a display section. As a display, a liquid crystal display, an organic EL display, a plasma display, etc. are mentioned, for example. When disposing the optical layered member of the present invention on the display part, it is disposed in such a manner that the anti-glare hard coat side formed on one side of the transparent support substrate is used as an outer layer, and the other side of the transparent support substrate or is laminated on the transparent support substrate. The decoration layer on the other side of the substrate is opposite to the surface of the display part. Thereby, the anti-glare hard coat layer will be arrange|positioned on the surface side of a display.

A preferred example of the above display may be a touch panel display. For example, it can be suitably used as an optical layered member for a touch panel display of an in-vehicle device. Example

The following examples illustrate the present invention in more detail, but the present invention is not limited thereto. In the examples, unless otherwise specified, "parts" and "%" are based on mass.

Preparation of stencil base material with concave-convex shape on the surface Production Example 1 Preparation of Acrylic Copolymer A Containing Unsaturated Double Bonds A mixture consisting of 171.6 parts of isobornyl methacrylate, 2.6 parts of methyl methacrylate and 9.2 parts of methacrylic acid was mixed. The mixed solution and 80.0 parts of propylene glycol monomethyl ether solution containing 1.8 parts of tertiary butyl peroxy-2-ethylhexanoate were titrated at the same time for 3 hours until they were equipped with stirring blades, nitrogen introduction pipes, After heating to 330.0 parts of methyl isobutyl ketone at 110° C. in a 1,000-ml reaction container with a cooling tube and a titration funnel, it was reacted at 110° C. for 30 minutes. Afterwards, titrate 0.2 parts of tertiary butyl peroxy-2-ethylhexanoate to a solution of 17.0 parts of propylene glycol monomethyl ether, then add 1.4 parts of tetrabutylammonium bromide and 5.0 parts of propylene glycol monomethyl ether solution containing 0.1 part of hydroquinone , While bubbling with air, the solution of 22.4 parts of 4-hydroxybutyl acrylate glycidyl ether and 5.0 parts of propylene glycol monomethyl ether was titrated for 2 hours, and then it was further reacted for 5 hours. An unsaturated double bond-containing acrylic copolymer A having a weight average molecular weight of 18,000 was obtained. The resin SP value: 10.0.

Production Example 2 Production of concave-convex shape forming paint composition 1 Add 37.5 parts of n-butanol, 24.88 parts of methyl ethyl ketone, 13.30 parts of ARONIX M-402 (di-neopentylthritol penta- and hexaacrylate manufactured by Toa Gosei Co., Ltd., SP value 12.1), CYCLOMER ACA-Z320M (DAICEL CORPORATION Acrylic acid acrylate, SP value 11.49) 15.52 parts, CAP-482-20 (EASTMAN CHEMICAL company's cellulose acetate, SP value 8.70) 2.66 parts and OMNIRAD 184 (IGM Resins company's photopolymerization initiator, 1-hydroxyl Cyclohexyl phenyl ketone) 1.42 parts and mixed and stirred. After that, 4.72 parts of unsaturated double bond-containing acrylic copolymer A was added while stirring, and the concave-convex shape forming coating composition 1 was prepared so that the solid content concentration was 25%.

Production Example 3 Preparation Example 1 of Template Substrate with Concavo-convex Shape The above concavo-convex forming composition 1 was coated on a 100 μm PET film (trade name A4300, manufactured by Toyobo Co., Ltd.) using a bar coater. Dry at 65°C for 1 minute to volatilize the solvent, and then irradiate it with ultraviolet rays with a cumulative light intensity of 1200mJ/ ^cm2 in an N ₂ gas environment to harden it to obtain a concave-convex shape with a film thickness of 2 μm and an external Hz of 22.1 %, Rzjis 0.51 μm template substrate 1.

Production Example 4 Preparation Example 2 of Template Substrate with Concavo-convex Shape The above concavo-convex forming composition 1 was coated on a 100 μm PET film (trade name A4300, manufactured by Toyobo Co., Ltd.) using a bar coater. Dry at 65°C for 1 minute to volatilize the solvent, and then irradiate it with ultraviolet rays with a cumulative light intensity of 2400mJ/ ^cm2 in an _N2 gas environment to harden it to obtain a concave-convex shape with a film thickness of 2μm and an external Hz of 22.4 %, Rzjis0.48μm template substrate 2.

Production Example 5 Preparation Example 3 of Template Substrate with Concavo-convex Shape The above concavo-convex forming composition 1 was coated on a 100 μm PET film (trade name A4300, manufactured by Toyobo Co., Ltd.) using a bar coater. Dry at 65°C for 1 minute to volatilize the solvent, and then irradiate it with ultraviolet rays with a cumulative light intensity of 600mJ/ ^cm2 in an N ₂ gas environment to harden it to obtain a concave-convex shape with a film thickness of 2 μm and an external Hz of 21.8 %, Rzjis0.49μm template substrate 3.

Production Example 6 Preparation Example 4 of Template Substrate with Concavo-convex Shape The above concavo-convex forming composition 1 was coated on a 100 μm PET film (trade name A4300, manufactured by Toyobo Co., Ltd.) using a bar coater. Dry at 65°C for 1 minute to volatilize the solvent, and then irradiate it with ultraviolet rays with a cumulative light intensity of 350mJ/ ^cm2 in an N ₂ gas environment to harden it to obtain a concave-convex shape with a film thickness of 2 μm and an external Hz of 23.1 %, Rzjis0.49μm template substrate 4.

Production Example 7 Production of Concave and Convex Shape Forming Paint Composition 2 Add 2.31 parts of methyl isobutyl ketone, 46.75 parts of isopropanol, 11.97 parts of ARONIX M-402 (manufactured by Toagosei Co., Ltd., SP value 12.1), and 11.97 parts of ARONIX M-305 (manufactured by Toagosei Co., Ltd., SP Value 12.7) 9.98 parts, ARONIX M-315 (Toagosei Co., Ltd., SP value 12.5) 11.97 parts, ARONIX M-220 (Toagosei Co., Ltd., SP value 12.2) 5.99 parts and OMNIRAD 184 (IGM Resins company system) 2.54 parts and mix and stir. After that, 8.49 parts of unsaturated double bond-containing acrylic copolymer A was added while stirring, and the concave-convex shape forming coating composition 2 was prepared so that the solid content concentration was 45%.

Production Example 8 Preparation Example 5 of Template Substrate with Concavo-convex Shape The above concavo-convex forming composition 2 was coated on a 100 μm PET film (trade name A4300, manufactured by Toyobo Co., Ltd.) using a bar coater. Dry at 80°C for 1 minute to volatilize the solvent, and then irradiate it with ultraviolet rays with a cumulative light intensity of 1200mJ/ ^cm2 in an _N2 gas environment to harden it to obtain a concave-convex shape with a film thickness of 2μm and an external Hz of 6.5 %, Rzjis0.29μm template substrate 5.

Production Example 9 Production of concave-convex shape forming paint composition 3 42.5 parts of n-butanol, 14.94 parts of methyl ethyl ketone, 19.98 parts of ethyl acetate, 7.98 parts of ARONIX M-402 (manufactured by Toagosei Co., Ltd., SP value 12.1), CYCLOMER ACA-Z320M (manufactured by DAICEL CORPORATION, SP value 11.49) 9.32 parts, CAP-482-20 (EASTMAN CHEMICAL, SP value 8.70) 1.60 parts, and OMNIRAD 184 (IGM Resins) 0.85 parts were mixed and stirred. Then, while stirring, 2.83 parts of acrylic copolymer A containing an unsaturated double bond was added to prepare a concave-convex shape forming coating composition 3 so that the solid content concentration was 15%.

Production Example 10 Preparation Example 6 of Template Substrate with Concavo-convex Shape The above concavo-convex forming composition 3 was coated on a 100 μm PET film (trade name A4300, manufactured by Toyobo Co., Ltd.) using a bar coater. Dry at 65°C for 1 minute to volatilize the solvent, and then irradiate it with ultraviolet rays with a cumulative light intensity of 1200mJ/ ^cm2 in an N ₂ gas environment to harden it to obtain a concave-convex shape with a film thickness of 2 μm and an external Hz of 34.7 %, Rzjis0.80μm template substrate 6.

Formation method of anti-glare hard coating Production Example 11 Preparation of Acrylic Copolymer B Containing Unsaturated Double Bonds The mixture consists of 30.0 parts of 2,3-epoxypropyl methacrylate, 35.8 parts of methyl methacrylate, 34.2 parts of isobornyl methacrylate and 0.3 parts of tertiary butylperoxy-2-ethylhexanoate the mixture. The mixture was titrated isokinetically over 2 hours to 70.0 parts of toluene heated to 110° C. under a nitrogen atmosphere in a 500 ml reaction vessel equipped with a stirring blade, a nitrogen introduction tube, a cooling tube, and a titration funnel. After the titration, the reaction was carried out at a temperature of 110° C. for 1 hour. Thereafter, 1.0 parts of tertiary butylperoxy-2-ethylhexanoate was titrated to a mixed solution of 25.0 parts of toluene over 1 hour. Thereafter, it was heated to 145° C., and after further reacting for 2 hours, it was cooled to 110° C. or lower, and 29.0 parts of toluene was added to obtain a precursor B1. 225.3 parts of precursor B1, 15.66 parts of acrylic acid, 0.43 parts of hydroquinone monomethyl ether and 56 parts of toluene were respectively fed into a 500ml reaction vessel equipped with stirring blades, air inlet pipes, cooling pipes and titration funnel, blowing in air and keeping aside Heat to 90°C while stirring. Under the temperature condition of 90 degreeC, the mixed solution of 3.0 parts of toluene and 0.81 parts of tetrabutylammonium bromide was added, and it was made to react for 1 hour. Then, it was heated to 105° C., and while confirming the acid value of the solid content in the reaction solution, the reaction was carried out at a temperature of 105° C. until the acid value was 8 or less. In addition, the acid value was calculated according to the following formula by titrating the above-mentioned reaction solution with a 0.1N potassium hydroxide (KOH) solution in accordance with JIS K5601-2-1. Acid value={(KOH solution titration [ml])×(KOH solution molar concentration [mol/L]}/(solid content mass [g]) Thereafter, a mixed solution of 0.43 parts of hydroquinone monomethyl ether and 3.0 parts of toluene was added to bring the temperature to 75° C., and a mixed solution of 10.1 parts of KarenzMOI (manufactured by Showa Denko), 5.0 parts of toluene, and 0.043 parts of dibutyltin dilaurate was added. React at a temperature of 70°C for 2 hours, then cool to below 60°C, add a mixed solution of 2.0 parts of methanol and 10.0 parts of toluene to obtain an unsaturated double bond-containing acrylic acid copolymer B with a weight average molecular weight of 350,000.

Example 1 Manufacturing method of hard coat composition 1 29.84 parts of propylene glycol monomethyl ether, 13.9 parts of ethyl acetate, 13.9 parts of butyl acetate, KRM-8452 (manufactured by DAICEL CORPORATION, polymerizable unsaturated group-containing urethane (meth)acrylate oligomer substance or polymer) 27.8 parts, OMNIRAD 184 (IGM Resins company, photopolymerization initiator, 1-hydroxycyclohexyl phenyl ketone) 0.98 parts, OMNIRAD TPO (IGM Resins company photopolymerization initiator, 2,4,6- Trimethylbenzoyldiphenylphosphine oxide) 1.31 parts, MIBK-AC-2140Z (manufactured by Nissan Chemical Co., Ltd., reactive colloidal silicon oxide, methyl isobutyl ketone dispersion of 40% by mass non-volatile matter) 12.27 part (solution dispersion state) and mixed and stirred, the hard coating composition 1 was prepared in the mode that the solid content concentration was 35%.

The production method of the anti-glare hard coating is 1.0mm thick and composed of PMMA (polymethyl methacrylate) and PC (polycarbonate) 3-layer (PMMA/PC/PMMA) sheet (trade name: MT3LTR, KURARAY Co., Ltd.) was coated with hard coat composition 1 with a bar coater so that the dry film thickness was 6 μm, and dried at 65° C. for 4 minutes to evaporate the solvent. Afterwards, use a laminator and use a pressing force of 0.5 MPa to make the hard-coated surface adhere to the concave-convex surface of the template base material in the above-mentioned preparation example 1 with a concave-convex shape. ^2. Ultraviolet radiation treatment to harden it, and then peel it off from the surface of the template substrate to obtain an anti-glare hard coating.

Example 2 Manufacturing method of hard coat composition 2 Add 29.84 parts of propylene glycol monomethyl ether, 7.94 parts of ethyl acetate, 7.95 parts of butyl acetate, Art Resin UN-905 (Urethane (methyl) containing polymerizable unsaturated groups manufactured by Negami Industry Co., Ltd. Acrylate oligomer or polymer) 39.72 parts, OMNIRAD 184 (manufactured by IGM Resins Co., Ltd.) 0.98 parts, OMNIRAD TPO (manufactured by IGM Resins Co., Ltd.) 1.31 parts, MIBK-AC-2140Z (manufactured by Nissan Chemical Co., Ltd.) 12.27 parts and mixed and stirred , a hard coat composition 2 was prepared so that the solid content concentration was 35%.

The production method of the anti-glare hard coating is on one side of a 1.0mm-thick three-layer (PMMA/PC/PMMA) sheet (trade name: MT3LTR, manufactured by KURARAY CO., LTD.) composed of PMMA and PC, using a rod The coating machine applied the hard coat composition 2 so that the dry film thickness was 6 μm, and dried it at 65° C. for 4 minutes to evaporate the solvent. Afterwards, use a laminator and use a pressing force of 0.5 MPa to make the hard-coated surface adhere to the concave-convex surface of the template base material in the above-mentioned preparation example 1 with a concave-convex shape. ^2. Ultraviolet radiation treatment to harden it, and then peel it off from the surface of the template substrate to obtain an anti-glare hard coating.

Example 3 Manufacturing method of hard coat composition 3 29.84 parts of propylene glycol monomethyl ether, 11.12 parts of ethyl acetate, 11.12 parts of butyl acetate, 22.24 parts of KRM-8452 (manufactured by DAICEL CORPORATION), UNIDIC V-6850 (manufactured by DIC Corporation, containing polymerizable unsaturated Acrylic acid (meth)acrylate oligomer or polymer) 11.12 parts, OMNIRAD 184 (manufactured by IGM Resins) 0.98 parts, OMNIRAD TPO (manufactured by IGM Resins) 1.31 parts, MIBK-AC-2140Z (manufactured by Nissan Chemical Co. 12.27 parts) were mixed and stirred to prepare a hard coating composition 3 so that the solid content concentration was 35%.

The production method of the anti-glare hard coating is on one side of a 1.0mm-thick three-layer (PMMA/PC/PMMA) sheet (trade name: MT3LTR, manufactured by KURARAY CO., LTD.) composed of PMMA and PC, using a rod The coating machine applied the hard coat composition 3 so that the dry film thickness was 6 μm, and dried it at 65° C. for 4 minutes to evaporate the solvent. Afterwards, use a laminator and use a pressing force of 0.5 MPa to make the hard-coated surface adhere to the concave-convex surface of the template base material in the above-mentioned preparation example 1 with a concave-convex shape. ^2. Ultraviolet radiation treatment to harden it, and then peel it off from the surface of the template substrate to obtain an anti-glare hard coating.

Example 4 Manufacturing method of hard coat composition 4 29.84 parts of propylene glycol monomethyl ether, 9.73 parts of ethyl acetate, 9.73 parts of butyl acetate, 19.46 parts of KRM-8452 (manufactured by DAICEL CORPORATION), 16.68 parts of UNIDIC V-6850 (manufactured by DIC Co., Ltd.), OMNIRAD 184 ( IGM Resins Co., Ltd.) 0.98 parts, OMNIRAD TPO (IGM Resins Co., Ltd.) 1.31 parts, MIBK-AC-2140Z (Nissan Chemical Co., Ltd.) 12.27 parts were mixed and stirred, and the hard coating composition was prepared so that the solid content concentration was 35%. Object 4.

The production method of the anti-glare hard coating is on one side of a 1.0mm-thick three-layer (PMMA/PC/PMMA) sheet (trade name: MT3LTR, manufactured by KURARAY CO., LTD.) composed of PMMA and PC, using a rod The coating machine applied the hard coat composition 4 so that the dry film thickness was 6 μm, and dried it at 65° C. for 4 minutes to evaporate the solvent. Afterwards, use a laminator and use a pressing force of 0.5 MPa to make the hard-coated surface adhere to the concave-convex surface of the template base material in the above-mentioned preparation example 1 with a concave-convex shape. ^2. Ultraviolet radiation treatment to harden it, and then peel it off from the surface of the template substrate to obtain an anti-glare hard coating.

Example 5 Production method of anti-glare hard coat on one side of a three-layer (PMMA/PC/PMMA) sheet (trade name: MT3LTR, manufactured by KURARAY CO., LTD.) with a thickness of 1.0mm and composed of PMMA and PC , The hard coat composition 3 was applied with a bar coater so that the dry film thickness was 6 μm, and dried at 65° C. for 4 minutes to evaporate the solvent. Afterwards, use a laminator and use a pressing force of 0.5 MPa to make the hard-coated surface adhere to the concave-convex surface of the template base material in the above-mentioned preparation example 2 with a concave-convex shape. ^2. Ultraviolet radiation treatment to harden it, and then peel it off from the surface of the template substrate to obtain an anti-glare hard coating.

Example 6 Production method of anti-glare hard coat layer On one side of a three-layer (PMMA/PC/PMMA) sheet (trade name: MT3LTR, manufactured by KURARAY CO., LTD.) with a thickness of 1.0 mm and composed of PMMA and PC , The hard coat composition 3 was applied with a bar coater so that the dry film thickness was 6 μm, and dried at 65° C. for 4 minutes to evaporate the solvent. Afterwards, use a laminator and use a pressing force of 0.5 MPa to make the hard-coated surface adhere to the concave-convex surface of the template substrate in the preparation example 3 of the template substrate with a concave-convex shape. The cumulative light intensity from the template substrate surface side is 1100mJ/cm ^2. Ultraviolet radiation treatment to harden it, and then peel it off from the surface of the template substrate to obtain an anti-glare hard coating.

Example 7 Production method of anti-glare hard coat layer On one side of a three-layer (PMMA/PC/PMMA) sheet (trade name: MT3LTR, manufactured by KURARAY CO., LTD.) with a thickness of 1.0mm and composed of PMMA and PC , The hard coat composition 3 was applied with a bar coater so that the dry film thickness was 6 μm, and dried at 65° C. for 4 minutes to evaporate the solvent. Afterwards, use a laminator and use a pressing force of 0.5 MPa to make the hard-coated surface adhere to the concave-convex surface of the template substrate of the aforementioned preparation example 4 with a concave-convex shape. The cumulative light intensity from the template substrate surface side is 1100mJ/cm ^2. Ultraviolet radiation treatment to harden it, and then peel it off from the surface of the template substrate to obtain an anti-glare hard coating.

Example 8 Production method of anti-glare hard coat layer On one side of a three-layer (PMMA/PC/PMMA) sheet (trade name: MT3LTR, manufactured by KURARAY CO., LTD.) with a thickness of 1.0 mm and composed of PMMA and PC , The hard coat composition 3 was applied with a bar coater so that the dry film thickness was 6 μm, and dried at 65° C. for 4 minutes to evaporate the solvent. Afterwards, use a laminator and use a pressing force of 0.006 MPa to make the hard-coated surface adhere to the concave-convex surface of the template substrate in the above-mentioned preparation example 1 with a concave-convex shape. The cumulative light intensity from the template substrate surface side is 1100mJ/cm ^2. Ultraviolet radiation treatment to harden it, and then peel it off from the surface of the template substrate to obtain an anti-glare hard coating.

Example 9 Production method of anti-glare hard coat layer On one side of a three-layer (PMMA/PC/PMMA) sheet (trade name: MT3LTR, manufactured by KURARAY CO., LTD.) with a thickness of 1.0mm and composed of PMMA and PC , The hard coat composition 3 was applied with a bar coater so that the dry film thickness was 6 μm, and dried at 65° C. for 4 minutes to evaporate the solvent. Afterwards, use a laminator and use a pressing force of 2.5 MPa to make the hard-coated surface and the concave-convex surface of the template base material in the preparation example 1 with a concave-convex shape. ^2. Ultraviolet radiation treatment to harden it, and then peel it off from the surface of the template substrate to obtain an anti-glare hard coating.

Example 10 Manufacturing method of hard coat composition 5 Add 29.84 parts of propylene glycol monomethyl ether, 11.1 parts of ethyl acetate, 11.1 parts of butyl acetate, 11.12 parts of UNIDIC V-6850 (manufactured by DIC Co., Ltd.), 22.24 parts of ARONIX M-402 (manufactured by Toagosei Co., Ltd.) into the container , 0.98 parts of OMNIRAD 184 (manufactured by IGM Resins), 1.31 parts of OMNIRAD TPO (manufactured by IGM Resins), 12.27 parts of MIBK-AC-2140Z (manufactured by Nissan Chemical Co., Ltd.) Hard coating composition 5 was produced.

The production method of the anti-glare hard coating is on one side of a 1.0mm-thick three-layer (PMMA/PC/PMMA) sheet (trade name: MT3LTR, manufactured by KURARAY CO., LTD.) composed of PMMA and PC, using a rod The coating machine applied the hard coat composition 5 so that the dry film thickness was 6 μm, and dried it at 65° C. for 4 minutes to evaporate the solvent. Afterwards, use a laminator and use a pressing force of 0.5 MPa to make the hard-coated surface adhere to the concave-convex surface of the template base material in the above-mentioned preparation example 1 with a concave-convex shape. ^2. Ultraviolet radiation treatment to harden it, and then peel it off from the surface of the template substrate to obtain an anti-glare hard coating.

Example 11 Production method of anti-glare hard coat layer on one side of a 1.0 mm thick three-layer (PMMA/PC/PMMA) sheet (trade name: MT3LTR, manufactured by KURARAY CO., LTD.) composed of PMMA and PC , The hard coat composition 3 was applied with a bar coater so that the dry film thickness was 6 μm, and dried at 65° C. for 4 minutes to evaporate the solvent. Afterwards, use a laminator and use a pressing force of 0.5 MPa to make the hard-coated surface adhere to the concave-convex surface of the template substrate in Example 5 of the aforementioned template substrate with a concave-convex shape. The cumulative light intensity from the template substrate surface side is 1100mJ/cm ^2. Ultraviolet radiation treatment to harden it, and then peel it off from the surface of the template substrate to obtain an anti-glare hard coating.

Example 12 Production method of anti-glare hard coat layer On one side of a three-layer (PMMA/PC/PMMA) sheet (trade name: MT3LTR, manufactured by KURARAY CO., LTD.) with a thickness of 1.0mm and composed of PMMA and PC , The hard coat composition 3 was applied with a bar coater so that the dry film thickness was 6 μm, and dried at 65° C. for 4 minutes to evaporate the solvent. Afterwards, use a laminator and use a pressing force of 0.5 MPa to bond the hard-coated surface to the concave-convex surface of the template substrate in Example 6 of the template substrate with a concave-convex shape. ^2. Ultraviolet radiation treatment to harden it, and then peel it off from the surface of the template substrate to obtain an anti-glare hard coating.

Example 13 Method for producing functional layer composition 1 912.7 parts of propylene glycol monomethyl ether, 5.36 parts of ARONIX M-402 (manufactured by Toagosei Co., Ltd.), 8.04 parts of Art Resin UN-906S (urethane acrylate produced by Negami Industry Co., Ltd.), OMNIRAD 127 (IGM Resins 1.88 parts made by the company) and 6.70 parts of OPTOOL DAC-HP (a fluorine-based additive manufactured by Daikin Industries, Ltd.) were mixed and stirred. While stirring, 65.33 parts of THRULYA 4320 (manufactured by Nikke Catalyst Chemicals Co., Ltd.) was added, and the functional layer composition 1 was prepared so that the solid content concentration was 3%.

The production method of the anti-glare hard coating is on one side of a 1.0mm-thick three-layer (PMMA/PC/PMMA) sheet (trade name: MT3LTR, manufactured by KURARAY CO., LTD.) composed of PMMA and PC, using a rod The coating machine applied the hard coat composition 3 so that the dry film thickness was 6 μm, and dried it at 65° C. for 4 minutes to evaporate the solvent. Afterwards, use a laminator and use a pressing force of 0.5 MPa to bond the hard-coated surface to the concave-convex surface of the template base material in Example 1 of the template base material with a concave-convex shape. ^2. Ultraviolet radiation treatment to harden it, and then peel it off from the surface of the template substrate to obtain an anti-glare hard coating. The above-mentioned functional layer composition 1 was coated on the concave-convex surface of the obtained anti-glare hard coat layer with a bar coater so that the dry film thickness was 80 nm, and dried at 65° C. for 1 minute to evaporate the solvent. Afterwards, it was hardened by ultraviolet irradiation treatment with a cumulative light quantity of 1500mJ/cm ² in an N ₂ gas environment to obtain an anti-glare hard coating layered with an organic functional layer.

Example 14 Manufacturing method of hard coat composition 6 7.36 parts of methyl isobutyl ketone, 29.84 parts of propylene glycol monomethyl ether, 10.70 parts of ethyl acetate, 10.71 parts of butyl acetate, 25.57 parts of KRM-8452 (manufactured by DAICEL CORPORATION), UNIDIC V-6850 (manufactured by DIC Co., Ltd. 12.79 parts of OMNIRAD 184 (manufactured by IGM Resins Co., Ltd.), 1.28 parts of OMNIRAD TPO (manufactured by IGM Resins Co., Ltd.), 0.80 parts of Techpolymer SSX-302ABE (manufactured by Sekisui Chemical Industry Co., Ltd., refractive index 1.595) and mixed Stirring was carried out to prepare a hard coating composition 6 so that the solid content concentration was 35%. Only the cured film of the adhesive resin had a refractive index of 1.51.

The measurement of the refractive index of the layer-forming resin component film contained in a hard-coat composition was performed using the Abbe's refractometer according to the method of JISK0062. The measurement of the light-transmitting fine particles is as follows: Prepare 3 types of light-transmitting fine particles in the layer-forming resin contained in the hard coating composition, and prepare different cured films, and then use an Abbe refractometer to measure Each refractive index. Calculate the refractive index of light-transmitting microparticles from the calibration curve.

The production method of the anti-glare hard coating is on one side of a 1.0mm-thick three-layer (PMMA/PC/PMMA) sheet (trade name: MT3LTR, manufactured by KURARAY CO., LTD.) composed of PMMA and PC, using a rod The coating machine applied the hard coat composition 6 so that the dry film thickness was 6 μm, and dried it at 65° C. for 4 minutes to evaporate the solvent. Afterwards, use a laminator and use a pressing force of 0.5 MPa to make the hard-coated surface adhere to the concave-convex surface of the template base material in the above-mentioned preparation example 1 with a concave-convex shape. ^2. Ultraviolet radiation treatment to harden it, and then peel it off from the surface of the template substrate to obtain an anti-glare hard coating.

Comparative example 1 Manufacturing method of hard coat composition 7 23.66 parts of propylene glycol monomethyl ether, 61.79 parts of acrylic acid copolymer B containing unsaturated double bonds, 0.98 parts of OMNIRAD 184 (manufactured by IGM Resins), 1.31 parts of OMNIRAD TPO (manufactured by IGM Resins), MIBK-AC- 2140Z (manufactured by Nissan Chemical Co., Ltd.) 12.27 was mixed and stirred, and the hard coating composition 7 was prepared so that the solid content concentration was 35%.

The production method of the anti-glare hard coating is on one side of a 1.0mm-thick three-layer (PMMA/PC/PMMA) sheet (trade name: MT3LTR, manufactured by KURARAY CO., LTD.) composed of PMMA and PC, using a rod The coating machine applied the hard coat composition 7 so that the dry film thickness was 6 μm, and dried it at 65° C. for 4 minutes to evaporate the solvent. Afterwards, use a laminator and use a pressing force of 0.5 MPa to make the hard-coated surface adhere to the concave-convex surface of the template base material in the above-mentioned preparation example 1 with a concave-convex shape. ^2. Ultraviolet radiation treatment to harden it, and then peel it off from the surface of the template substrate to obtain an anti-glare hard coating.

Comparative example 2 Manufacturing method of hard coat composition 8 29.84 parts of propylene glycol monomethyl ether, 13.9 parts of ethyl acetate, 13.9 parts of butyl acetate, 27.8 parts of ARONIX M-305 (neopentyritol tri- and tetraacrylate manufactured by Toagosei Co., Ltd.), and OMNIRAD 184 were placed in a container. (manufactured by IGM Resins Co., Ltd.), 0.98 parts of OMNIRAD TPO (manufactured by IGM Resins Co., Ltd.), 12.27 parts of MIBK-AC-2140Z (manufactured by Nissan Chemical Co., Ltd.) were mixed and stirred, and a hard coat was prepared so that the solid content concentration was 35%. Composition 8.

The production method of the anti-glare hard coating is on one side of a 1.0mm-thick three-layer (PMMA/PC/PMMA) sheet (trade name: MT3LTR, manufactured by KURARAY CO., LTD.) composed of PMMA and PC, using a rod The coating machine applied the hard coat composition 8 so that the dry film thickness was 6 μm, and dried it at 65° C. for 4 minutes to evaporate the solvent. Afterwards, use a laminator and use a pressing force of 0.5 MPa to make the hard-coated surface adhere to the concave-convex surface of the template base material in the above-mentioned preparation example 1 with a concave-convex shape. ^2. Ultraviolet radiation treatment to harden it, and then peel it off from the surface of the template substrate to obtain an anti-glare hard coating.

Comparative Example 3 Production method of antiglare hard coat layer on one side of a three-layer (PMMA/PC/PMMA) sheet (trade name: MT3LTR, manufactured by KURARAY CO., LTD.) with a thickness of 1.0 mm and composed of PMMA and PC , The hard coat composition 3 was applied with a bar coater so that the dry film thickness was 6 μm, and dried at 65° C. for 4 minutes to evaporate the solvent. Afterwards, use a laminator to bond the hard-coated surface to the concave-convex surface of the template substrate in Preparation Example 1 of the above-mentioned concave-convex template substrate with a pressing force of 0.0005 MPa. The cumulative light intensity from the template substrate surface side is 1100mJ/cm ^2. Ultraviolet radiation treatment to harden it, and then peel it off from the surface of the template substrate to obtain an anti-glare hard coating.

Comparative Example 4 Manufacturing method of hard coat layer On one side of a 3-layer (PMMA/PC/PMMA) sheet (trade name: MT3LTR, manufactured by KURARAY CO., LTD.) with a thickness of 1.0mm and composed of PMMA and PC, use The bar coater coated the hard coat composition 3 with a dry film thickness of 6 μm, dried it at 65°C for 4 minutes to evaporate the solvent, and irradiated it with ultraviolet rays with a cumulative light intensity of 1100mJ/ ^cm2 under a nitrogen atmosphere. After hardening, it is peeled off from the surface of the template substrate to obtain a hard coat layer.

Comparative Example 5 Manufacturing method of hard coat layer On one side of a 3-layer (PMMA/PC/PMMA) sheet (trade name: MT3LTR, manufactured by KURARAY CO., LTD.) with a thickness of 1.0mm and composed of PMMA and PC, use The unevenness forming composition 1 was coated with a bar coater so that the dry film thickness was 2 μm, dried at 65°C for 4 minutes to evaporate the solvent, and then irradiated with ultraviolet rays with a cumulative light intensity of 1200mJ/ ^cm2 under a nitrogen atmosphere to make it After hardening, it is peeled off from the surface of the template substrate to obtain a hard coat layer.

Comparative example 6 In the manufacture of the anti-glare hard coat layer, after coating the hard coat composition 3 and drying it, after bonding the uneven surface of the template base material 1, the template base material is peeled off without ultraviolet radiation, and after peeling, ultraviolet radiation is performed, Except for this, a hard coat layer was obtained in the same procedure as in Example 3.

Comparative Example 7 Manufacturing method of hard coat composition 9 Add 29.84 parts of propylene glycol monomethyl ether, 13.9 parts of ethyl acetate, 13.9 parts of butyl acetate, and 27.8 parts of ARONIX M-315 (Isocyanuric acid EO-modified di- and triacrylate manufactured by Toya Gosei Co., Ltd.) into the container , 0.98 parts of OMNIRAD 184 (manufactured by IGM Resins Co., Ltd.), 1.31 parts of OMNIRAD TPO (manufactured by IGM Resins Co., Ltd.), and 12.27 parts of MIBK-AC-2140Z (manufactured by Nissan Chemical Co., Ltd.) were mixed and stirred to prepare a solid content concentration of 35%. A hard coat composition 9 is produced.

The production method of the anti-glare hard coating is on one side of a 1.0mm-thick three-layer (PMMA/PC/PMMA) sheet (trade name: MT3LTR, manufactured by KURARAY CO., LTD.) composed of PMMA and PC, using a rod The coating machine applied the hard coat composition 9 so that the dry film thickness was 6 μm, and dried it at 65° C. for 4 minutes to evaporate the solvent. Afterwards, use a laminator and use a pressing force of 0.5 MPa to make the hard-coated surface adhere to the concave-convex surface of the template base material in the above-mentioned preparation example 1 with a concave-convex shape. ² UV irradiation treatment to harden it. Afterwards, an attempt was made to peel off the base material surface of the template, but it was not possible to peel off and an anti-glare hard coat layer could not be obtained.

The following evaluation tests were carried out using the anti-glare hard coatings obtained in the above Examples and Comparative Examples. The evaluation results are shown in the table below.

Calculation of film thickness The measurement of the film thickness was performed as follows. The test sample was cut into 10mm×10mm, and the cross-section of the coating film was precipitated with a microtome (LEICA RM2265). The deposited cross-section was observed with a laser microscope (manufactured by VK8700 KEYENCE), and the film thickness at 10 points of the concave portion and 10 points of the convex portion was measured, and the average value was calculated to obtain the film thickness.

Determination method of pressing pressure during surface contact A pressure-sensitive sheet (Prescale, manufactured by Fuji Film Co., Ltd.) was placed on the transparent support substrate to measure the pressing force of the laminator.

Determination of peel strength before/after hardening Cut the template base material, transparent support base material and anti-glare hard coating into a width of 25 mm and a length of 200 mm. In an atmosphere of 23°C and 50RH%, measure and peel off one end of the template base material at a fixed speed of 300 mm/min for 180 degrees. The intensity of time.

Visual Appearance Evaluation Put the test sample of the anti-glare hard coating under the fluorescent lamp, and visually confirm the surface layer of the anti-glare hard coating. Appearance evaluation criteria after bonding are as follows. ○: No floating, sinking, height difference, or extrusion of the coating film was observed in the bonded film. ×: Floating, sinking, height difference, and extrusion of the coating film were observed in the laminated film. The evaluation criteria of the appearance after peeling are as follows. ◯: Concave-convex appearance was uniformly provided over the entire surface, and no step difference or extrusion of the coating film was observed. ×: The transparent part which is not transferred to the unevenness, the level difference, and the extrusion of the coating film can be observed.

Determination of the ten-point average roughness Rz _JIS of the anti-glare hard coating surface Cut the test sample of the anti-glare hard coating to 50mm×50mm, and use a laser with an eyepiece magnification of 20 times and an objective lens magnification of 50 times A microscope (manufactured by VK8700 KEYECE) was measured in accordance with JIS B0601; 2001 to obtain an Rz _jis value.

Concave-convex shape transfer rate The concavo-convex shape transfer rate of the test sample of the antiglare hard-coat layer was calculated|required by the following procedure. First, measure the Rz _JIS (A) value of the template substrate in the same order as above. Under the pressing pressure range of 0.001~5MPa, press the concave-convex surface of the stencil substrate on the surface of the unhardened hard coating to make surface contact, and in the state of surface contact of the stencil substrate, the amount of light is accumulated 1100mJ/cm ² irradiates ultraviolet rays to harden the unhardened hard coating. The template substrate was peeled off from the obtained hard coat layer, and Rz _JIS (B) of the formed concave-convex shape surface was measured. Using Rz _JIS (A) of the template base material and Rz _JIS (B) of the formed uneven surface, the uneven shape transfer rate was obtained from the following formula (B)/(A)×100(%).

Determination of haze value of anti-glare hard coating The haze value (total haze value) of the antiglare hard coat layer was measured using a haze meter (NDH2000 manufactured by Nippon Denshoku Co., Ltd.) and the haze value Ha of the antiglare hard coat layer was measured in accordance with JIS K7136.

Determination of total light transmittance of anti-glare hard coating Measure the incident light intensity (T0) of the anti-glare hard coating and the total transmitted light intensity (T1) of the anti-glare hard coating, and calculate the total light transmittance (Tt (%)) of the anti-glare hard coating by the following formula. Tt(%)=T1/T0×100

Determination of average length RSm of curve elements of surface roughness of anti-glare hard coating Using a laser microscope (manufactured by VK-8700 KEYENCE, etc.), in accordance with JIS B0601; 2001, measure the average length RSm of the roughness curve elements on the surface of the anti-glare hard coating.

Image quality evaluation of anti-glare hard coating Using the image quality tester ICM-1T (manufactured by Suga Test Instruments Co., Ltd.), the anti-glare hard The amount of light transmitted by the coating. The width ratio of the light part and the dark part in the optical comb is 1:1, and the width n (mm) is 0.125, 0.25, 0.5, 1 and 2, and the moving speed is 10mm/min. In the measurement test of the clarity of the transmitted image, the maximum amount of transmitted light when there is a transmission part of the optical comb (bright place) on the optical axis is Mn, and the minimum amount of transmitted light is when there is a light-shielding part of the optical comb (dark place) on the optical axis The value is mn, and the transmission image clarity Cn (%) at this time is calculated by the following formula. Cn={(Mn-mn)/(Mn+mn)}×100 Next, the total value Tc (%) is obtained. When the width n(mm) of the optical comb is 0.125, 0.25, 0.5, 1 and 2 respectively, the total value Tc(%) is 5 transmission image clarity C0.125(%), C0.25(%), C0. The sum of 5(%), C1(%) and C2(%) (the maximum possible value is 500%).

Determination of Pencil Hardness According to JIS K 5600-5-4, the pencil hardness of the coating film was measured. Specifically, it measures using a pencil scratch coating film hardness tester (manufactured by Toyo Seiki Seisakusho, type P, pressurized load 100 g to 1 kg). Use a pencil for the scratch value test made by Mitsubishi Uni (tested by the Japan Paint Testing Association), and use abrasive paper (3M P-1000) to adjust the tip of the lead to a smooth and circular cross section. After setting the sample on the measuring table, fix the pencil so that the scratching angle is 45°, and carry out the test under the condition of a load of 750g. For each test, the test point was staggered while smoothing the refill, and the test was repeated 5 times. The presence or absence of dents on the surface of the coating film was confirmed visually. For example, when a 3H pencil is used for the test and no scratch occurs, it is judged to be 3H or more. When slight sinking was observed in 1 test out of 5 tests, it was judged as 3H. Then, when sinking was observed in 2 or more of the 5 tests, it was judged to be less than 3H, and the same evaluation was performed in a step down. When the pencil hardness is less than 3H, it can be judged that the hardness and scratch resistance are not good.

Scratch resistance test With a load of 2N or 4N per 2cm ² , make steel wool #0000 go back and forth 10 times on the surface of the anti-glare hard coating to carry out the scratch resistance test. Use a microscope with a magnification of 100 times (manufactured by KEYENCE CORPORATION, digital microscope VHX-2000, lens Z2100) to observe the surface of the sample after the scratch resistance test, and judge the field of view of the microscope according to the following criteria. ⊚: Under a load of 4 N per 2 cm ² , no flaws with a length of 500 μm or more were observed at all. ◯: Under a load of 2 N per 2 cm ² , no flaws with a length of 500 μm or more were observed at all. △: Under the load of 2N per 2cm ² , at least 1~5 scars with a length of 500μm or more were observed. ×: Under a load of 2 N per 2 cm ² , multiple scars with a length of 500 μm or more were observed.

Glare Evaluation Using a display with a pixel density of 326ppi, the following evaluation criteria were used to visually evaluate the test samples of the anti-glare hard coating. ◎: Glare is hardly recognized but good. ○: Good although a little glare can be recognized. Δ: Recognition of glare is poor. X: The glare is not well recognized clearly.

Anti-glare evaluation A black PET film (manufactured by PANAC Co., Ltd., trade name: Gelpoly GPH100E82A04) and a test sample of an anti-glare coating were bonded together to prepare a test piece. Put the test piece under the fluorescent light to check the reflection degree of the fluorescent light visually. The evaluation criteria are as follows. ○: The outline of the reflected fluorescent lamp is distorted. △: The outline of the reflected fluorescent lamp is slightly distorted. X: The outline of the reflected fluorescent lamp was recognized.

In addition, the external haze value (external Hz) of the template base material was measured in the following procedure. Haze value (total haze value) of template base material Using a haze meter (NDH2000 manufactured by Nippon Denshoku), the total haze value Ha of the template base material was measured according to the method of JIS K7136. Cut the test sample of template base material into 50mm×50mm. Titrate 0.01ml of glycerin (special grade reagent, manufactured by KISHIDA CHEMICAL Co., Ltd.) on the concave and convex surface of the test sample, and then mount it on a glass plate (18mm×18mm, manufactured by Songlang Glass Co., Ltd.) Test piece with uneven surface. Using the aforementioned haze meter, the internal haze value Hi of the template substrate was measured in accordance with JIS K7136. The external haze value H was measured by the following calculation formula. External haze value H=Ha-Hi

In addition, among the evaluation items of the anti-glare hard coat layer of Example 13 with the functional layer, the items of "Rz _JIS " and "transfer rate of concave-convex shape" were evaluated in the state before the functional layer was installed, and the other items were It is evaluated in the state after setting the functional layer.

[Table 1]

[Table 2]

[table 3]

Any of the anti-glare hard coat layers formed in the examples has a high transfer rate of concave-convex shapes, and it has been confirmed that they have good anti-glare performance. And these anti-glare hard coatings have been further confirmed to have high hardness and a very high value of the total value (%) of the clarity of the transmitted image. Comparative Example 1 is an illustration in which the weight average molecular weight of the polymer containing polymerizable unsaturated groups contained in the hard coating composition exceeds the range of Claim 1. In this example, the peel strength (peel strength before curing) of the contact portion between the uneven surface of the template base material and the uncured hard coat surface was reduced, and the uneven shape could not be transferred well. Comparative Example 2 is an illustration of a hard coating composition that does not contain polymerizable unsaturated group-containing oligomers or polymers. In this example, the peel strength (peel strength before hardening) of the contact portion between the uneven surface of the stencil substrate and the uncured hard coat surface is small, and the coating film is extruded from the end, resulting in uneven film thickness. The embossed shape cannot be transferred well. Comparative Example 3 is an example where the pressing pressure is less than 0.001 MPa when one surface is in contact. In this example, voids were generated between the template base material and the anti-glare hard coat layer, and the transfer of the concave-convex shape could not be confirmed in the gap portion, and the concave-convex shape could not be transferred satisfactorily. Comparative Example 4 is an example without performing the surface contact step of the template substrate. In this example, a hard coat layer having no concavo-convex shape was formed. Comparative Example 5 is an example formed without using a template base material, which uses concave-convex shape forming coating composition 1 used to form the template base material instead of the hard coating composition. In this example, the hardness of the hard coat is less than 3H. Comparative Example 6 is an example of peeling off the template substrate and then irradiating it with ultraviolet rays after making surface contact between the template substrate and the uncured hard coat layer without irradiating ultraviolet rays. In this example, when the template substrate was peeled off, a part of the anti-glare hard coat layer adhered to the film inseparably, and the concave-convex shape could not be transferred well. Comparative Example 7 is an illustration of a hard coating composition that does not contain polymerizable unsaturated group-containing oligomers or polymers, and uses polymerizable unsaturated group-containing monomers with higher viscosity. In this example, the template substrate could not be peeled after ultraviolet irradiation, and the template substrate peel strength after ultraviolet irradiation could not be measured. Industrial availability

According to the forming method of the present invention, it is possible to form an anti-glare hard coating having a concave-convex shape that can exhibit good anti-glare performance and excellent scratch resistance. The anti-glare hard coating formed by the present invention can be suitable for such as high-resolution displays.

(none)

Claims (12)

A method for forming an anti-glare hard coating, which is provided on at least one side of a transparent support substrate with an anti-glare hard coating with a concave-convex shape on the surface, comprising the following steps: a template substrate manufacturing step, which manufactures the surface Concavo-convex template base material; coating step, which is coated with a hard coating composition on one side of the transparent support base material to form an unhardened hard coat layer; surface contact step, which uses the concave-convex shape of the aforementioned template base material The two substrates are brought into surface contact in the direction where the shape surface is opposite to the surface of the aforementioned unhardened hard coat layer; a hardening step of irradiating active energy rays to harden the unhardened hard coat layer; and a peeling step of removing the template base material Peel off from the hardened hard coat layer; and, the aforementioned hard coat composition includes polymerizable unsaturated group-containing oligomers or polymers with a weight average molecular weight in the range of 1,000 to 200,000; the concave-convex shape of the aforementioned template substrate and The peel strength of the surface contact part of the unhardened hard coat surface is in the range of 0.01~2N/25mm; after active energy ray irradiation, the peel strength of the concave-convex shape surface of the template substrate and the surface contact part of the hard coat layer is 0.005 Within the range of ~1.5N/25mm; and in the surface contact step between the concave-convex shape surface of the template substrate and the unhardened hard coating surface, the pressing pressure is 0.001~5MPa, and the concave-convex shape transfer when the pressing pressure is within the aforementioned range The rate is 75~100%. The method for forming an anti-glare hard coating as in Claim 1, wherein the concave-convex shape on the surface of the template substrate is formed in the following manner: coating the concave-convex shape-forming coating composition containing the first component and the second component, and then The first component and the second component are phase-separated. The method for forming an anti-glare hard coat as claimed in claim 1, wherein the aforementioned hard coat composition comprises: the polymerizable unsaturated group-containing oligomer or polymer with a weight average molecular weight in the range of 1,000 to 200,000; and polymerizable a polymerizable unsaturated group-containing monomer having an unsaturated group equivalent of 90 to 500 g/eq; The amount of the oligomer or polymer is 15-85 parts by mass, and the amount of the aforementioned polymerizable unsaturated group-containing monomer is 85-15 parts by mass. The method for forming an antiglare hard coat according to any one of claims 1 to 3, wherein the polymerizable unsaturated group of the polymer containing a polymerizable unsaturated group is selected from acryl and methacryl One or more of the groups formed. The method for forming an anti-glare hard coat according to any one of claims 1 to 3, wherein the hardness of the anti-glare hard coat is 2H or higher in pencil hardness. The method for forming an anti-glare hard coat according to any one of claims 1 to 3, wherein the anti-glare hard coat with a concave-convex surface has a ten-point average roughness Rz _JIS of 0.2 to 1.0 μm and a roughness curve The average length RSm of the element is the surface uneven shape of 5~100μm. The method for forming an anti-glare hard coat according to any one of claims 1 to 3, wherein the hard coat composition further contains light-transmitting fine particles with an average particle diameter of 0.5-10 μm, and the refractive index of the light-transmitting fine particles is (Rf1) and the refractive index (Rf2) of the layer-forming resin component contained in the aforementioned hard coat composition satisfy the following relationship: 0.01≦|Rf1-Rf2|≦0.23. The method for forming an anti-glare hard coating according to any one of Claims 1 to 3, wherein the anti-glare hard coating with a concave-convex shape on the surface has: 0.125mm, 0.25mm, 0.5mm, 1.0mm and 2.0mm The surface concave-convex shape of the total value (%) of the transmission image sharpness (%) of the five kinds of widths of the optical comb is in the range of 300~480. The method for forming an anti-glare hard coat according to any one of Claims 1 to 3, after the aforementioned stripping step, further comprises a step of forming a functional layer on the concave-convex surface of the obtained anti-glare hard coat, and the The functional layer is one or more selected from the group consisting of a high-refractive-index layer, a low-refractive-index layer, and an antifouling layer. The method for forming an anti-glare hard coat according to any one of Claims 1 to 3, further comprising: a decorative layer forming step, which is to form a decorative layer on the other side of the transparent support substrate. A method of manufacturing a display with an anti-glare hard coating, comprising the step of disposing the anti-glare hard coating on the surface of the display, and the anti-glare hard coating is obtained by the method according to any one of claims 1 to 10 . Such as the display with anti-glare hard coating of claim 11 The manufacturing method, wherein the aforementioned display is a touch panel display.